Supplementary Material

Save this PDF as:
 WORD  PNG  TXT  JPG

Size: px
Start display at page:

Download "Supplementary Material"

Transcription

1 ARKIVC 0 (iii) S-S9 Supplementary Material Lewis acid-catalyzed Diels-Alder reaction of -cyclopentenones with Danishefsky s diene: double bond isomerization of tetrahydro-hindene-,(7ah)-diones, and attempts on an asymmetric catalysis Michael Krebs and Sabine Laschat* Institut für rganische Chemie, Universität Stuttgart, Pfaffenwaldring, D-709 Stuttgart, Germany Dedicated to Prof. Rainer Beckert on the occasion of his 0th birthday Contents NMR spectroscopic analysis of double bond isomers 0, Details on the isolation of ketals, Synthesis of the proline-based oxazaborolidines a-d S S S9 Page S

2 ARKIVC 0 (iii) S-S9 NMR-spectroscopic analysis of the inseparable double bond isomers 0, The NMR-spectroscopic analysis of the isolated mixture of double bond isomers 0 and is discussed in the following: Initially we expected the two compounds to be the two regioisomers 0 and as shown below. 7 7a a 7 7a a 0 Scheme S If indeed the regioisomers 0 and were formed, we should have found a multiple degenerated doublet in the range of and 7 ppm in the H-NMR spectrum for each of the vinylic protons -H and 7-H (regioisomer 0) and -H und -H (regioisomer ) respectively. As shown in the enlargement of the olefinic part of the H-NMR spectrum between.80 and. ppm in Figure S, the NMR experiment provided a doublet of doublets (J = 0. Hz, J =. Hz) at.8 ppm and a doublet of doublets of doublets (J = 0. Hz, J =. Hz, J = 0.7 Hz) at. ppm. The third multiplet at. ppm was identified to be a triplet of doublets of doublets (J =.7 Hz, J =. Hz, J = 0.7 Hz). The integration of the triplet of doublets of doublets showed a value of one whereas the doublet of doublets of doublets and the doublet of doublets contained an integration of 0.7 each. This and the fact that both had an identical coupling constant (0. Hz) led us to the assumption that these two protons are located in the same molecule. The triplet of doublets of doublets was then inevitably assigned to the second compound. n closer examination of the integration we found a ratio of 0.7:.7 or 0.:0.7 of the two isomers that is attended by GC analysis (cf. Table ). Conflicting our first theory of the two regioisomers 0 and was the fact that we found only three signals for the four expected vinylic protons and the presence of nearly equimolar mixtures made us suspicious of the supposed structure of the two isolated products. Page S

3 ARKIVC 0 (iii) S-S9 tdd (J =.7 Hz, J =. Hz, J = 0.7 Hz). ppm H dd (J = 0. Hz, J =. Hz).8 ppm 0.7 H ddd (J = 0. Hz, J =. Hz, J = 0.7 Hz). ppm 0.7 H Figure S H-NMR spectrum of the inseparable mixture of double bond isomers 0, In order to explore the real structures of the two compounds the HSQC spectrum of the mixture was examined carefully. A sector of the HSQC spectrum is shown in Figure S. ne of the carbon atoms (9. ppm) in the vinylic part of the spectrum shows no cross peak to any of the protons. Therefore it was assigned as a quaternary carbon. This assumption was confirmed in a DEPT-spectrum that is not shown here. Page S

4 ARKIVC 0 (iii) S-S9 Figure S HSQC spectrum of the inseparable mixture of double bond isomers 0, At this point it was clear that one of the compounds had a quaternary olefinic carbon atom and owing to the two olefinic protons the other compound had to be one of the two initially expected ones. Altogether there were four possible isomers (Scheme S). 7a a 7 7a a 7 7a a 7 7a a 7 0 0' ' Schema S The next issue was the position of the double bond. In order to solve that problem, the HMBC spectrum was investigated more closely. Possible correlations between the olefinic protons -H and 7-H (isomers 0, 0 ) and -H, -H (isomers, ) respectively, and the carbonyl carbon atoms C-, C- (isomers 0, 0 ) and C-, C- (isomers, ) respectively, should be observed in that spectrum and so the problem of the position of the double bond Page S

5 ARKIVC 0 (iii) S-S9 should be resolved unambiguously. In the case of isomer 0 there should be a cross peak of the protons -H and 7-H to both of the carbonyl C-atoms C- and C- whereas in the case of isomer the olefinic protons -H and -H should correlate only to one of the carbonyl C-atoms, namely C-. The same applies for the isomers 0 and. A correlation of the olefinic proton 7-H to both of the carbonyl carbons should be detected in the case of isomer 0 and only one cross peak should be seen in the case of isomer. A part of the HMBC spectrum is shown in Figure S. Figure S HMBC spectrum of the inseparable mixture of double bond isomers 0, The olefinic protons at. ppm (ddd) and. ppm (tdd) are unambiguously correlated to two C-atoms. This verifies the structure of the two double bond isomers, that is about the two compounds 0 and 0 (= ) (Scheme S). It is not uncommon that there is no correlation in the HMBC-spectrum between the dd at.8 ppm and the carbonyl C-atoms, since such two-bondcouplings are not always visible in these HMBC spectra. Page S

6 ARKIVC 0 (iii) S-S9 + Me SiMe ) LA ) H + + 9a 0 0' = Scheme S This result also explains why there was obtained only one product in the selective reduction of the enone moiety. Details on the isolation of ketals, In the following the isolation of the pure monoketal and diketal and their NMR spectroscopic analysis is specified: As described in the main part the obtained monoketal and the bisketal could not be separated by chromatography (Scheme S). But initially the structure of the two isolated products (one with m/z 9, the other with m/z ) was not confirmed at least four different monoketals d and two different diketals, b were possible (Scheme S). b + 0 Ethylenglycol PPTS benzene 00 C, h c m/z 9 d b m/z 8 Scheme S Page S

7 ARKIVC 0 (iii) S-S9 We felt confident that after reduction of the enone moiety of the monoketal to the corresponding alcohol, the remaining diketal could be separated from the resulting alcohol. The mixture of the monoketal and diketal was reduced with equiv. NaBH in the presence of 0. equiv. LiCl in CH CN. Actually we obtained after reduction a mixture of diketal and diasteriomeric allylic alcohols (Scheme S). The desired diketal could then be separated via preparative HPLC and analyzed in NMR experiments. The NMR sample, dissolved in CDCl, was subjected to another GC-MS analysis and we found out that the compound was not the same anymore than before the NMR experiment: Under the slightly acid conditions of CDCl one of the ketal protecting groups was cleaved off. This resulting monoketal showed exactly the same retention time as the monoketal gained during the first ketalization and so we assumed that the two monoketals had the same structure. There is shown the olefinic section of the resulting H-NMR of the obtained monoketal in Figure S. ddd (J = 0. Hz, J =. Hz, J = 0.9 Hz).8 ppm H dd (J = 0. Hz, J =. Hz).7 ppm H Figure S H-NMR spectrum of the obtained monoketal Comparison of the NMR spectrum with the starting material 0, revealed that the ketalization took exclusively place with the C/C7 double bond isomer rather than the C7/C7a isomer. There are visible two signals: ne doublet of doublets (.7 ppm, J = 0. Hz, J =. Hz) and one doublet of doublets of doublets (.8 ppm, J = 0. Hz, J =. Hz, J = 0.9 Hz). The Page S7

8 ARKIVC 0 (iii) S-S9 position of the ketal was determined by comparison of the chemical shifts of the carbonyl carbon in the C-NMR spectrum with the C-NMR spectrum of the double bond isomer 0. It is well known that carbonyl carbons in -membered rings are detected at lower field (approx. 0-0 ppm) whereas conjugated carbonyl carbons are detected at higher field (approx ppm). The double bond isomer 0 shows the carbonyl C-atom in the -membered ring at. ppm whereas the conjugated carbonyl carbon in the -membered ring shows up at 9. ppm. The carbonyl C-atom in the described monoketal shows one signal at 9.9 ppm. We concluded that the carbonyl carbon must be the one conjugated in the -membered ring (Scheme S). CDCl Ethylenglycol PPTS + benzene 00 C, h 0 NaBH,LiCl CH CN, rt, min H H H H H H a b Scheme S The olefinic part of the H-NMR spectrum of the diketal, dissolved in benzene-d is shown in Figure S. Again a doublet of doublets (.7 ppm, J = 0. Hz, J =. Hz) and a doublet of doublets of doublets (. ppm, J = 0. Hz, J =. Hz, J = 0.7 Hz) was observed. Since the difference of the chemical shifts (v v ) J, the two signals are distorted. Again the similarity of the spectrum to the one of double bond isomer 0 is evident. Thus the structures of the resulting monoketal and the diketal could be established. Page S8

9 ARKIVC 0 (iii) S-S9 dd (J = 0. Hz, J =.).7 ppm H ddd (J = 0. Hz, J =. Hz, J = 0.7 Hz). ppm H Figure S H-NMR spectrum of the obtained diketal Synthesis of the proline-based oxazaborolidines a-d : (S)-N-(Ethoxycarbonyl)-proline methyl ester (7) N 7 L-Proline (.00 g,. mmol) was dissolved in 8 ml of methanol. Potassium carbonate (.97 g,. mmol) was added and the mixture was cooled to 0 C. Then 9 ml (0. g, 9.0 mmol) ethyl chloroformate were added slowly. The resulting solution was allowed to warm up to room temperature and was stirred for further h. The resulting colorless solid was filtered off, the solvent was reduced in vacuo and the remaining colorless oil was transferred to 0 ml of H. Then ml of CH Cl were added and the layers were separated. The aqueous layer was extracted with x 0 ml CH Cl and the combined Page S9

10 ARKIVC 0 (iii) S-S9 organic layers were dried over MgS. Concentration under reduced pressure afforded the product as colorless oil (7. g, 8 mmol, 87%). A mixture of rotamers was obtained. H-NMR (00 MHz, CDCl ): δ =.0 (t, J = 7. Hz, H, CH CH ),.7 (t, J = 7. Hz, H, CH CH ),.8 -. (m, 8H, -H, -H), (m, H, -H),.7 (s, H, CH ),.7 (s, H, CH ),.0. (m, H, CH CH ),. (dd, J =., J = 8. Hz, H, -H),.7 (dd, J =., J = 8. Hz, H, -H) ppm. C-NMR (7 MHz, CDCl ): δ =. (CH CH ),.7 (CH CH ),.,., 9.9, 0.9 (C-, C- ),.,.7 (C-),.,. (CH ), 8.8, 9.0 (C-),.,. (CH ),.,. (C-), 7., 7. (C-) ppm. Spectroscopic data were consistent with previously reported data for this compound. (S)-N-Ethoxy-α,α-diphenyl--pyrrolidinemethanol (8) N 8 H In an oven dried Schlenk flask 7. g (0.0 mol) magnesium turnings were covered with 7 ml of THF. A small amount of bromobenzene ( ml, 0.0 mol) was added to the mixture and the reaction was started using a heat gun. Then a mixture of.8 ml (0.7 g, 0. mol) bromobenzene and ml of THF was added dropwise and after complete addition the grey solution was refluxed for further 0 min. Under an inert gas atmosphere (S)-N-(ethoxcarbonyl)proline methyl ester (7) (7. g, 7.8 mmol) was dissolved in 7 ml THF and cooled to 0 C. The Grignard-solution was added slowly over a period of one hour and the resulting solution was stirred for further 0 h at room temperature. The reaction was hydrolyzed using 0 ml sat. NaHC solution. After the addition of 00 ml of dichloromethane the layers were separated and the aqueous layer was extracted with x ml CH Cl. The combined organic layers were dried over MgS and concentrated in vacuo. Purification by flash chromatography (: hexanes/ethyl acetate) afforded the product as a colorless solid (.0 g,. mmol, 0%). Page S0

11 ARKIVC 0 (iii) S-S9 H-NMR (00 MHz, CDCl ): δ = 0.8 (b, H, -H a ),. (t, J = 7. Hz, H, CH CH ),.. (m, H, -H a ), (m, H, -H b ),.0. (m, H, -H b ),.9 (m, H, -H a ),..7 (m, H, -H b ),.0.8 (m, H, CH CH ),.9 (dd, J =.8, J = 8.8 Hz, H, - H), (m, 0H, Ph) ppm. C-NMR (7 MHz, CDCl ): δ =. (CH CH ),.0, 9.7 (C-, C-), 7.7 (C-),.9 (CH CH ),.9 (C-), 8. (C-), 7., 7., 7., 7., 7.9, 8. (Ph),.7 (ArC),. (C-) ppm. Spectroscopic data were consistent with previously reported data for this compound. (S)-α,α-Diphenyl--pyrrolidinemethanol (9) NH 9 H (S)-N-Ethoxy-α,α-diphenyl--pyrrolidinemethanol (8) (.0 g,. mmol) was dissolved in ml of methanol. Potassium hydroxide (7.0 g, 0. mol) was added and the resulting solution was refluxed for 0 h. After concentration the resulting yellow oil was transferred to 0 ml H and 0 ml of dichloromethane were added. The layers were separated and the aqueous layer was extracted with x 0 ml CH Cl. The combined organic layers were washed with brine, dried over MgS and concentrated in vacuo. After recrystallization from ml of heptane.0 g (0.00 mol, 8%) of a colorless solid were obtained. H-NMR (00 MHz, CDCl ): δ =.0.8 (m, H, -H, -H), (m, H, -H),. (t, J = 7. Hz, H, -H), (m, 0H, Ph) ppm. C-NMR (7 MHz, CDCl ): δ =.,. (C-, C-),.8 (C-),. (C-), 77. (C-),.,.9,.,., 8.0, 8. (Ph),. (ArC), 8. (ArC) ppm. [α] D 0 = -. (c = 0., MeH) [Lit.: -. (c = 0., MeH)] Spectroscopic data were consistent with previously reported data for this compound. Page S

12 ARKIVC 0 (iii) S-S9 (S)-Ethyl -(hydroxydinaphthalen--ylmethyl)pyrrolidine--carboxylate (0), (S)-,-Di(naphthalen--yl)tetrahydropyrrolo[,-c]oxazol-(H)-one () In an oven dried Schlenk flask 0.0 g (.7 mmol) magnesium turnings were covered with 0 ml of THF. A small amount of -bromonaphthalene (0.0 g,.0 mmol) in ml of THF was added to the reaction mixture. The reaction was started using one crystal of iodine. Then a mixture of.99 g (9. mmol) -bromonaphthalene and 8 ml of THF was added dropwise and after complete addition the grey solution was refluxed for further three hours. Then 0. g (.0 mmol) (S)-N-(ethoxycarbonyl)proline methyl ester (7) were dissolved in 0 ml of THF and cooled to 0 C. Since the Grignard-solution was poorly soluble in cold THF, it was dissolved in hot benzene. The addition of the Grignard-solution was completed after one hour and the mixture was stirred for further 0 h at room temperature. The reaction was hydrolyzed using 0 ml sat. NaHC solution. After the addition of 0 ml of dichloromethane the layers were separated and the aqueous layer was extracted with x ml CH Cl. The combined organic layers were dried over MgS and concentrated in vacuo. Purification by flash chromatography (: hexanes/ethyl acetate) afforded 0.0 g (%) of a mixture (:) of desired product 0 and the cyclic carbamate. H N 0 R f = 0. (: hexanes/ethyl acetate, anisaldehyde) H-NMR (00 MHz, CDCl ): δ = 0.79 (b, H, -H a ),.0 (t, J =.8 Hz, H, CH CH ),.0. (m, H, -H a ),.0.9 (m, H, -H b, -H b ),.90.0 (m, H, -H a ),..0 (m, H, -H b ),.0.8 (m, H, CH CH ),. (dd, J =.0, J = 8.7 Hz, H, -H), (m, H, Ar), (m, 8H, Ar) ppm. C-NMR (7 MHz, CDCl ): δ =.8 (CH CH ),., 0.0 (C-, C-), 8.0 (C-),. (CH CH ),. (C-), 8. (C-),.,.,.,.,., 7., 7., 7., 7.7, 8.0, 8.7, 8.9 (Ph),.78,.8,.0,. (ArC),.8 (C-) ppm. Spectroscopic data were consistent with previously reported data for this compound. Page S

13 ARKIVC 0 (iii) S-S9 N R f = 0. (: hexanes/ethyl acetate, anisaldehyde) H-NMR (00 MHz, CDCl ): δ =.. (m, H, -H a ),.7.78 (m, H, -H b ),.8.9 (m, H, -H a ),.9.0 (m, H, H b ),.7. (m, H, -H a ),.7.80 (m, H, - H b ),.77 (dd, J =., J = 0. Hz, H, -H), 7. (dd, J =.9, J = 8. Hz, H, Ar), (m, H, Ar), 7. (dd, J =., J = 8. Hz, H, Ar), (m, H, Ar), 8.0 (d, J =. Hz, H, Ar), 8.0 (d, J =. Hz, H, Ar) ppm. C-NMR (7 MHz, CDCl ): δ =.0, 9. (C-, C-),. (C-), 8.7 (C-), 8. (C-),.8,.0,.,.,.9,.,.,.7, 7., 7., 8., 8., 8., 8.7 (Ph),.,.8,.9,.0, 7., 0. (ArC), 0. (C-) ppm. Spectroscopic data were consistent with previously reported data for this compound. (S)-α,α-Di--naphthyl--pyrrolidinemethanol () NH H The mixture of (S)-,-di(naphthalen--yl)tetrahydropyrrolo[,-c]oxazol-(H)-one and (S)-ethyl -(hydroxydinaphthalen--ylmethyl)pyrrolidine--carboxylate 0 (0.8 g,. mmol) was dissolved in 0 ml of methanol and an excess of potassium hydroxide (.0 g, 0.0 mol) was added. The mixture was stirred for h at room temperature, methanol was distilled off and the residue was dissolved in ml of dichloromethane. Water was added ( ml), the layers were separated and the organic layer was dried over MgS. After concentration in vacuo 0.7 g (0.7 mmol, 80%) of desired product was isolated as a colorless solid. Page S

14 ARKIVC 0 (iii) S-S9 H-NMR (00 MHz, CDCl ): δ =.0.8 (m, H, -H, -H, NH),.97. (m, H, -H),. (t, J = 7., H, -H), (br, H, H), (m, H, Ar), 7.8 (dd, J =.8, J = 8.7 Hz, H, Ar), (m, H, Ar), (m, H, Ar), (m, H, Ar) ppm. C-NMR (7 MHz, CDCl ): δ =.,. (C-, C-),.9 (C-),.0 (C-), 77. (C-),.8,.0,.,.,.,.8,.9,., 7., 7.7, 8., 8., 8., (Ph),.0,.,.,.,.,., (ArC) ppm. Spectroscopic data were consistent with previously reported data for this compound. 7 (S)-Ethyl -(-naphthoyl)pyrrolidine--carboxylate () N In an oven dried Schlenk flask. g (0.8 mol) magnesium turnings were covered with 0 ml of THF. A small amount of -bromonaphthalene (0. g,. mmol) in ml of THF was added to the reaction mixture. The reaction was started using one crystal of iodine. Then a mixture of 7.8 g (8.0 mmol) -bromonaphthalene and 0 ml of THF was added drop wise and after complete addition the grey solution was refluxed for further three hours. Then. g (.0 mmol) (S)-N-(ethoxycarbonyl)proline methyl ester 7 were dissolved in 0 ml of THF and cooled to 0 C. Since the obtained Grignard-solution was poorly soluble in cold THF, it was dissolved in hot benzene. The addition of the Grignard-solution was completed after one hour and the mixture was stirred for further h at room temperature. The reaction was hydrolyzed using 00 ml sat. NaHC solution. After the addition of 00 ml of dichloromethane the layers were separated and the aqueous layer was extracted with x ml CH Cl. The combined organic layers were dried over MgS and concentrated in vacuo. Purification by flash chromatography (: hexanes/ethyl acetate) afforded. g (%) of monoarylated product. R f = 0. (: hexanes/ethyl acetate, anisaldehyde) btained was a mixture of two rotamers. Page S

15 ARKIVC 0 (iii) S-S9 H-NMR (00 MHz, CDCl ): δ =. (t, J = 7. Hz, H, CH CH ),. (t, J = 7. Hz, H, CH CH ),.88.7 (m, 8H, -H, -H),.. (m, H, -H),.7.8 (m, H, -H),. (q, J = 7. Hz, H, CH CH ),.0 (q, J = 7. Hz, H, CH CH ),. (dd, J =.7, J = 8.9 Hz, H, -H),. (dd, J =.7, J = 8.9 Hz, H, -H), (m, H, Ar), (m, H, Ar), 8.0 (d, J = 8. Hz, H, Ar), 8. (d, J = 8. Hz, H, Ar) ppm. C-NMR (7 MHz, CDCl ): δ =.,.8 (CH CH ),.,., 9., 0. (C-, C-),.8, 7. (C-),.,. (CH CH ),.0,. (C-),.,.,.,.,.,.7, 7.0, 7., 7.9, 8.0, 8., 8., 0.,.,.,.8,.9,.8,. (Ar),.,. (C-), 0., 0. (C-) ppm. HRMS (ESI): calcd. for C 8 H 9 N Na +, 0. found 0.7. MS (APCI) m/z: 98. [M + H] +,. [M C H ],. [M CC H ], 08.,.0,., 7.0,.0, 98.0, 70.. FT-IR (ATR): ν = 979 (w), 8 (s), 9 (m), 80 (w), (m), (w), 7 (m), 0 (m), 00 (w), 98 (m), 887 (m), 777 (m), 70 (m) cm -. [α] D 0 = -.0 (c =.0, CH Cl ) (7aS)--(naphthalen--yl)--phenyltetrahydropyrrolo[,-c]oxazol-(H)-one () N In an oven dried Schlenk flask 88. mg (. mmol) magnesium turnings were covered with 0 ml of THF. A small amount of bromobenzene (0.0 ml, 0.0 g, 0.0 mmol) in ml of THF was added to the reaction mixture. The reaction was started using one crystal of iodine. In the following a mixture of 0. ml (0. g,.0 mmol) bromobenzene and ml of THF was added dropwise and after complete addition the grey solution was refluxed for further three hours. Then 0.7 g (0.9 mmol) (S)-Ethyl -(-naphthoyl)pyrrolidine--carboxylate were dissolved in ml of THF and cooled to 0 C. The obtained Grignard-solution was added slowly over a period of one hour and the resulting solution was stirred for further 0 h at room temperature. Page S

16 ARKIVC 0 (iii) S-S9 The reaction was hydrolyzed using 0 ml sat. NaHC solution. After the addition of 0 ml of dichloromethane the layers were separated and the aqueous layer was extracted with x ml CH Cl. The combined organic layers were dried over MgS and concentrated in vacuo. Purification by flash chromatography (: hexanes/ethyl acetate) afforded the product as a colorless solid (0.0 g, 0.0 mmol, %). R f = 0. (: hexanes/ethyl acetate, anisaldehyde) H-NMR (00 MHz, CDCl ): δ = (m, H, -H a ),.8.0 (m, H, -H b ),.7.9 (m, H, -H),.. (m, H, -H a ),.7.8 (m, H, -H b ),.9 (dd, J =., J = 0.9 Hz, H, -H), (m, H, Ar), (m, H, Ar), 7.7 (dd, J = 7., J = 8. Hz, H, Ar), (m, H, Ar), 8.0 (d, J =. Hz, H, Ar), 8.08 (dd, J =., J = 7. Hz, H, Ar) ppm. C-NMR (7 MHz, CDCl ): δ =., 8. (C-, C-),. (C-), 9. (C-), 8. (C-),.,.,.,.,.9, 7.0, 8.8, 8.9, 9., 9. (Ar), 9.,.,.,. (ArC), 0. (C-) ppm. HRMS (ESI): calcd. for C H 9 N Na +., found.. MS (ESI) m/z:. [M + Na] +, 0. [M + H] +, 8., 9., 9.,.. FT-IR (ATR): ν = 09 (w), 97 (w), (w), 78 (s), 98 (w), 09 (w), 8 (w), 7 (m), 0 (m), 09 (m), 9 (m), 80 (m), 778 (m) cm -. [α] D 0 = -8. (c = 0.8, CH Cl ) (S)-α,α-(-Naphthyl)-phenyl--pyrrolidinemethanol () NH H (7aS)--(Naphthalen--yl)--phenyltetrahydropyrrolo[,-c]oxazol-(H)-one (0.07 g, 0. mmol) was dissolved in ml of methanol and an excess of potassium hydroxide (0.0 g, 9.00 Page S

17 ARKIVC 0 (iii) S-S9 mmol) was added. The mixture was refluxed for h, methanol was distilled off and the residue was dissolved in ml of dichloromethane. Water was added ( ml), the layers were separated and the organic layer was dried over MgS. After concentration in vacuo 0.0 g (0.0 mmol, 9%) of desired product was isolated as a yellow oil. H-NMR (00 MHz, CDCl ): δ =..0 (m, H, -H, -H),.8.9 (m, H, -H a ),.0 -. (m,h, -H b ),.0.9 (m, H, -H), (m, H, Ar), (m, H, Ar), (m, H, Ar), (m, H, Ar), 8.0 (br, H, Ar) ppm. C-NMR (7 MHz, CDCl ): δ =.8, 7. (C-, C-),. (C-),.8 (C-), 79. (C-),.,.,.,.,.9,., 7.9, 8., 8.0 (Ph),.7,.8, 0., 7.7 (ArC) ppm. HRMS (ESI): calcd. for C 8 H 9 N, 0.70 found 0.9 [M + H] +. MS (ESI) m/z: 0.7 [M + H] +, 8. [M H]. FT-IR (ATR): ν = 89 (s), 0 (s), 08 (m), 90 (s), 70 (m), 0 (w), 7 (m) cm -. [α] D 0 = -0.0 (c = 0.0, CH Cl ) mp.: C (S)-N-Ethoxy-α,α-dimethyl--pyrrolidinemethanol () H N In an oven dried Schlenk flask.9 g (0.08 mol) magnesium turnings were covered with 0 ml of diethyl ether. A small amount of methyl iodide (0. ml, 0.7 g,.00 mmol) was added to the mixture and the reaction was started using a heat gun. In the following a mixture of.8 ml (.97 g,.0 mol) methyl iodide and ml of Et was added drop wise and after complete addition the colorless solution was refluxed for further 0 minutes. Under an inert gas atmosphere (S)-N-(ethoxcarbonyl)proline methyl ester 7 (.00 g,.9 mmol) was dissolved in 0 ml Et and cooled to 0 C. The obtained Grignard-solution was added slowly over a period of one hour and the resulting solution was stirred for further 0 h at room temperature. The reaction was hydrolyzed using 0 ml sat. NaHC solution. After the addition of 0 ml of dichloromethane the layers were separated and the aqueous layer was extracted with Page S7

18 ARKIVC 0 (iii) S-S9 x 0 ml CH Cl. After drying over MgS concentration afforded.00 g (.9 mmol, 00%) of the desired product as yellow oil. H-NMR (00 MHz, CDCl ): δ =.07 (s, H, Me),.7 (s, H, Me),.7 (t, J = 7., H, CH CH ),.9.0 (m, H, -H, -H),..7 (m, H, -H a ),..79 (m, H, - H b ),.89 (t, J = 7., H, -H),. (q, J = 7., H, CH CH ),.7 (br, H, H) ppm. C-NMR (7 MHz, CDCl ): δ =.8 (CH CH ),.,. (C-, C-), 7.8, 9. (Me), 8. (C-),.9 (CH CH ), 7.9 (C-), 7.8 (C-), 8. (C-) ppm. Spectroscopic data were consistent with previously reported data for this compound. 8 (S)-α,α-Dimethyl--pyrrolidinemethanol (7) H NH 7 (S)-N-Ethoxy-α,α-dimethyl--pyrrolidinemethanol (0.0 g,.8 mmol) was dissolved in 0 ml of methanol and an excess of potassium hydroxide (.8 g, 0.08 mol) was added. The mixture was refluxed for h, methanol was distilled off and the residue was dissolved in ml of dichloromethane. Water was added ( ml), the layers were separated and the organic layer was dried over MgS. After concentration in vacuo 0.0 g (0.77 mmol, %) of desired product was isolated as a yellow oil. H-NMR (00 MHz, CDCl ): δ =.09 (s, H, Me),. (s, H, Me), (m, H, -H, -H),.8.0 (m, H, -H, -H) ppm. C-NMR (7 MHz, CDCl ): δ =.9,.9 (C-, C-),., 7. (Me),.8 (C-),. (C-), 9. (C-) ppm. Spectroscopic data were consistent with previously reported data for this compound. 9 Tri(o-tolyl)boroxin (8) o-tolylboronic acid (0.9 g,.80 mmol) was dissolved in 0 ml of toluene, heated to 0 C and was directly distilled off via a claisen bridge. This procedure was repeated three times. The favored product was obtained as a colorless solid (0. g,.8 mmol, 8%). Page S8

19 ARKIVC 0 (iii) S-S9 B B B 8 H-NMR (00 MHz, CDCl ): δ =.8 (s, H, Me) (m, H), 7. (td, J = 7., J =. Hz, H), 8.0 (dd, J = 7., J =. Hz, H) ppm. C-NMR (7 MHz, CDCl ): δ =.,., 0.,., 7.,. ppm. Spectroscopic data were consistent with previously reported data for this compound. 0. Nyberg, N. T.; Duus, J. Ø.; Sorensen,. W. J. Am. Chem. Soc ,.. Halimjani, A. Z.; Saidi, M. R. Synth. Commun. 00,, 7.. Kalinowski, H.; Berger, S.; Braun, S. C-NMR-Spektroskopie, Georg Thieme Verlag, Stuttgart, Germany 98,.. Gautier, F. M.; Martin, S. J.; Jones, S. rg. Biomol. Chem. 009, 7, 9.. Mathre, D. J.; Jones, T. K.; Xavier, L. C. ; Blacklock, T. J.; Reamer, R. A.; Mohan, J. J.; Turner Jones, E. T.; Hoogsteen, K.; Baum, M. W.; Grabowsky E. J. J. J. rg. Chem. 99,, 7.. Ho, C.-Y.; Chen, Y.-C.; Wong, M.-K.; Yang D. J. rg. Chem. 00, 70, Corey, E. J.; Link, J.. Tet. Lett. 989, 0, Sibi, M. P.; Manyem, S. rg. Lett. 00,, Sibi, M. P.; Zhang, R.; Manyem, S. J. Am. Chem. Soc. 00,, (a) Corey, E. J.; Loh, T. P. J. Am. Chem. Soc. 99,, 89; (b) Corey, E.J.; Shibata, T.; Lee, T. W. J. Am. Chem. Soc. 00,, 808. Page S9

Synthesis of Trifluoromethylated Naphthoquinones via Copper-Catalyzed. Cascade Trifluoromethylation/Cyclization of. 2-(3-Arylpropioloyl)benzaldehydes

Synthesis of Trifluoromethylated Naphthoquinones via Copper-Catalyzed. Cascade Trifluoromethylation/Cyclization of. 2-(3-Arylpropioloyl)benzaldehydes Supporting Information to Synthesis of Trifluoromethylated Naphthoquinones via Copper-Catalyzed Cascade Trifluoromethylation/Cyclization of 2-(3-Arylpropioloyl)benzaldehydes Yan Zhang*, Dongmei Guo, Shangyi

More information

Efficient Mono- and Bis-Functionalization of 3,6-Dichloropyridazine using (tmp) 2 Zn 2MgCl 2 2LiCl ** Stefan H. Wunderlich and Paul Knochel*

Efficient Mono- and Bis-Functionalization of 3,6-Dichloropyridazine using (tmp) 2 Zn 2MgCl 2 2LiCl ** Stefan H. Wunderlich and Paul Knochel* Efficient Mono- and Bis-Functionalization of 3,6-Dichloropyridazine using (tmp) 2 Zn 2Mg 2 2Li ** Stefan H. Wunderlich and Paul Knochel* Ludwig Maximilians-Universität München, Department Chemie & Biochemie

More information

Tetrahydrofuran (THF) was distilled from benzophenone ketyl radical under an argon

Tetrahydrofuran (THF) was distilled from benzophenone ketyl radical under an argon SUPPLEMENTARY METHODS Solvents, reagents and synthetic procedures All reactions were carried out under an argon atmosphere unless otherwise specified. Tetrahydrofuran (THF) was distilled from benzophenone

More information

Supporting Information. (1S,8aS)-octahydroindolizidin-1-ol.

Supporting Information. (1S,8aS)-octahydroindolizidin-1-ol. SI-1 Supporting Information Non-Racemic Bicyclic Lactam Lactones Via Regio- and cis-diastereocontrolled C H insertion. Asymmetric Synthesis of (8S,8aS)-octahydroindolizidin-8-ol and (1S,8aS)-octahydroindolizidin-1-ol.

More information

Carbonylative Coupling of Allylic Acetates with. Arylboronic Acids

Carbonylative Coupling of Allylic Acetates with. Arylboronic Acids Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2015 Carbonylative Coupling of Allylic Acetates with Arylboronic Acids Wei Ma, a Ting Yu, Dong Xue,*

More information

Suzuki-Miyaura Coupling of Heteroaryl Boronic Acids and Vinyl Chlorides

Suzuki-Miyaura Coupling of Heteroaryl Boronic Acids and Vinyl Chlorides Suzuki-Miyaura Coupling of Heteroaryl Boronic Acids and Vinyl Chlorides Ashish Thakur, Kainan Zhang, Janis Louie* SUPPORTING INFORMATION General Experimental: All reactions were conducted under an atmosphere

More information

Supporting Information

Supporting Information Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2017 Supporting Information Palladium-Catalyzed Oxidative Allylation of Bis[(pinacolato)boryl]methane:

More information

Supporting Information

Supporting Information Supporting Information Wiley-VCH 2007 69451 Weinheim, Germany (TMP) 2 Zn 2MgCl 2 2LiCl: A ew Highly Chemoselective Base for the Directed Zincation of Sensitive Aromatics and Heteroaromatics** Stefan H.

More information

Supporting Information

Supporting Information Supporting Information ACA: A Family of Fluorescent Probes that Bind and Stain Amyloid Plaques in Human Tissue Willy M. Chang, a Marianna Dakanali, a Christina C. Capule, a Christina J. Sigurdson, b Jerry

More information

Supporting Information. Expeditious Construction of the DEF Ring System of Thiersinine B

Supporting Information. Expeditious Construction of the DEF Ring System of Thiersinine B Supporting Information Expeditious Construction of the DEF Ring System of Thiersinine B Masaru Enomoto and Shigefumi Kuwahara* Laboratory of Applied Bioorganic Chemistry, Graduate School of Agricultural

More information

SYNTHESIS OF A 3-THIOMANNOSIDE

SYNTHESIS OF A 3-THIOMANNOSIDE Supporting Information SYNTHESIS OF A 3-THIOMANNOSIDE María B Comba, Alejandra G Suárez, Ariel M Sarotti, María I Mangione* and Rolando A Spanevello and Enrique D V Giordano Instituto de Química Rosario,

More information

Supporting Information. for. A two step synthesis of a key unit B precursor of. cryptophycins by asymmetric hydrogenation

Supporting Information. for. A two step synthesis of a key unit B precursor of. cryptophycins by asymmetric hydrogenation Supporting Information for A two step synthesis of a key unit B precursor of cryptophycins by asymmetric hydrogenation Benedikt Sammet, Mathilde Brax and Norbert Sewald* Address: Bielefeld University,

More information

Tuning Porosity and Activity of Microporous Polymer Network Organocatalysts by Co-Polymerisation

Tuning Porosity and Activity of Microporous Polymer Network Organocatalysts by Co-Polymerisation Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2014 Supporting Information Tuning Porosity and Activity of Microporous Polymer Network Organocatalysts

More information

Supporting Information for. An Approach to Tetraphenylenes via Pd-Catalyzed C H Functionalization

Supporting Information for. An Approach to Tetraphenylenes via Pd-Catalyzed C H Functionalization Supporting Information for An Approach to Tetraphenylenes via Pd-Catalyzed C H Functionalization Hang Jiang, Yu Zhang, Dushen Chen, Bo Zhou, and Yanghui Zhang * Department of Chemistry, and Shanghai Key

More information

How to build and race a fast nanocar Synthesis Information

How to build and race a fast nanocar Synthesis Information How to build and race a fast nanocar Synthesis Information Grant Simpson, Victor Garcia-Lopez, Phillip Petemeier, Leonhard Grill*, and James M. Tour*, Department of Physical Chemistry, University of Graz,

More information

Cis Trans Proline Isomerization Effects on Collagen Triple-Helix Stability are Limited

Cis Trans Proline Isomerization Effects on Collagen Triple-Helix Stability are Limited Cis Trans Proline Isomerization Effects on Collagen Triple-Helix Stability are Limited an Dai and Felicia A. Etzkorn* Department of Chemistry, Virginia Tech, Blacksburg, VA 24061-0212 Supporting Information.

More information

Supporting Information for: End-capping ROMP Polymers with Vinyl. Lactones

Supporting Information for: End-capping ROMP Polymers with Vinyl. Lactones Supporting Information for: End-capping RMP Polymers with Vinyl Lactones Stefan Hilf, Robert H. Grubbs and Andreas F.M. Kilbinger * Institut für rganische Chemie, Johannes Gutenberg-Universität Mainz,

More information

SUPPLEMENTARY INFORMATION

SUPPLEMENTARY INFORMATION doi:10.1038/nature22309 Chemistry All reagents and solvents were commercially available unless otherwise noted. Analytical LC-MS was carried out using a Shimadzu LCMS-2020 with UV detection monitored between

More information

Supporting Information

Supporting Information Intramolecular hydrogen-bonding activation in cysteines. New effective radical scavenging Luisa Haya, a Iñaki Osante, b Ana M. Mainar, a Carlos Cativiela, b Jose S. Urieta*,a a Group of Applied Thermodynamics

More information

Supplementary Information. Low volume shrinkage polymers by photo Polymerization of 1,1- Bis(ethoxycarbonyl)-2-vinylcyclopropanes

Supplementary Information. Low volume shrinkage polymers by photo Polymerization of 1,1- Bis(ethoxycarbonyl)-2-vinylcyclopropanes Electronic Supplementary Material (ESI) for Polymer Chemistry. This journal is The Royal Society of Chemistry 2015 Supplementary Information Low volume shrinkage polymers by photo Polymerization of 1,1-

More information

with EDCI (5.73 g, 30.0 mmol) for 10 min. Bromoethylamine hydrobromide (6.15

with EDCI (5.73 g, 30.0 mmol) for 10 min. Bromoethylamine hydrobromide (6.15 2. A solution of Rhodamine B (14.2 g, 30.0 mmol) in CH 2 Cl 2 (40 ml) was treated with EDCI (5.73 g, 30.0 mmol) for 10 min. Bromoethylamine hydrobromide (6.15 g, 30.0 mmol) and TEA (4.21 ml, 3.03 g, 30.0

More information

Synthesis of borinic acids and borinate adducts using diisopropylaminoborane

Synthesis of borinic acids and borinate adducts using diisopropylaminoborane Synthesis of borinic acids and borinate adducts using diisopropylaminoborane Ludovic Marciasini, Bastien Cacciuttolo, Michel Vaultier and Mathieu Pucheault* Institut des Sciences Moléculaires, UMR 5255,

More information

Yields refer to analytically pure samples. Isomer ratios were determined by suitable

Yields refer to analytically pure samples. Isomer ratios were determined by suitable Supporting Information Sustainable Radical Reduction through Catalytic Hydrogen Atom Transfer Andreas Gansäuer,* Chun-An Fan, Frederik Piestert Kekulé-Institut für Organische Chemie und Biochemie der Universität

More information

Supporting Information

Supporting Information Electronic upplementary Material (EI) for Journal of Materials Chemistry B. This journal is The Royal ociety of Chemistry 216 upporting Information A dual-functional benzobisthiadiazole derivative as an

More information

Supporting Information. Rh (III)-Catalyzed Meta-C H Olefination Directed by a Nitrile Template

Supporting Information. Rh (III)-Catalyzed Meta-C H Olefination Directed by a Nitrile Template Supporting Information Rh (III)-Catalyzed Meta-C H Olefination Directed by a Nitrile Template Hua-Jin Xu, Yi Lu, *, Marcus E. Farmer, Huai-Wei Wang, Dan Zhao, Yan-Shang Kang, Wei-Yin Sun, *, Jin-Quan Yu

More information

SUPPLEMENTARY INFORMATION

SUPPLEMENTARY INFORMATION doi:10.1038/nature12761 Materials and Methods General Unless otherwise noted, all reactions were carried out under an atmosphere of argon, and all reagents were purchased from commercial suppliers and

More information

Supplementary Figure 1. 1 H and 13 C NMR spectra for compound 1a

Supplementary Figure 1. 1 H and 13 C NMR spectra for compound 1a 216.29 185.02 164.20 148.97 128.19 87.70 79.67 77.30 77.04 76.79 74.66 26.23 2.02 2.03 2.01 3.05 7.26 6.92 6.90 6.25 6.23 5.61 5.60 5.58 5.25 5.24 1.58 Supplementary Figure 1. 1 H and 13 C NMR spectra

More information

Stereoselective Synthesis of a Topologically Chiral Molecule: The Trefoil Knot

Stereoselective Synthesis of a Topologically Chiral Molecule: The Trefoil Knot Stereoselective Synthesis of a Topologically Chiral Molecule: The Trefoil Knot Laure-Emmanuelle Perret-Aebi, Alexander von Zelewsky 1, Christiane Dietrich- Buchecker and Jean-Pierre Sauvage Bis-5,6-pinene

More information

Diastereoselectivity in the Staudinger reaction of. pentafluorosulfanylaldimines and ketimines

Diastereoselectivity in the Staudinger reaction of. pentafluorosulfanylaldimines and ketimines Supporting Information for Diastereoselectivity in the Staudinger reaction of pentafluorosulfanylaldimines and ketimines Alexander Penger, Cortney. von ahmann, Alexander S. Filatov and John T. Welch* Address:

More information

Supporting Information. Contents

Supporting Information. Contents Supporting Information Rhodium-Catalyzed Selective Mono- and Di-Amination of Arenes with Single Directing Site On Water Md Ashif Ali,, Xiayin Yao,, Guigen Li, and Hongjian Lu, * Contents Schemes S1-S9...2

More information

Supporting Information. Stereoselective Syntheses of Trisubstituted Olefins via Platinum Catalysis α- Silylenones with Geometrical Complementarity

Supporting Information. Stereoselective Syntheses of Trisubstituted Olefins via Platinum Catalysis α- Silylenones with Geometrical Complementarity Supporting Information Stereoselective Syntheses of Trisubstituted lefins via Platinum Catalysis α- Silylenones with Geometrical Complementarity Douglas A. Rooke and Eric M. Ferreira* Department of Chemistry,

More information

Supporting Information

Supporting Information Supporting Information Wiley-VCH 2008 69451 Weinheim, Germany Supporting Information Unmasking Representative Structures of TMP-Active Hauser and Turbo Hauser Bases Pablo García-Álvarez, David V. Graham,

More information

A Closer Look at the Bromine-Lithium Exchange with

A Closer Look at the Bromine-Lithium Exchange with SUPPRTIG IFRMATI A Closer Look at the Bromine-Lithium Exchange with tert-butyllithium in an Aryl Sulfonamide Synthesis Christopher Waldmann,*, tmar Schober, Günter Haufe, and Klaus Kopka, Department of

More information

Supporting Information

Supporting Information Supporting Information Catalyst- and solvent-free one-pot synthesis of some novel polyheterocycles from aryldiazenyl salicylaldehyde derivatives Narsidas J. Parmar 1, Rikin A. Patel 1, Shashikant B. Teraiya

More information

Coupling with Aryl and Heteroaryl Iodides

Coupling with Aryl and Heteroaryl Iodides Regioselective Zincation of Indazoles using TMP 2 Zn 2LiCl and egishi Cross- Coupling with Aryl and Heteroaryl Iodides Andreas Unsinn and Paul Knochel* Ludwig Maximilians-Universität München, Department

More information

Supporting Information

Supporting Information Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2018 Supporting Information Content Synthesis of compounds 2a, 2b in Scheme

More information

Supporting Information

Supporting Information Supporting Information for Engineering of indole-based tethered biheterocyclic alkaloid meridianin into -carboline-derived tetracyclic polyheterocycles via amino functionalization/6-endo cationic π-cyclization

More information

Supporting Information

Supporting Information Supporting Information Iridium-Catalyzed Highly Regioselective Azide-Ynamide Cycloaddition to Access 5-Amido-Fully-Substituted 1,2,3-Triazoles under Mild, Air, Aqueous and Bioorthogonal Conditions Wangze

More information

Distyrylbenzene-aldehydes: identification of proteins in water. Supporting Information

Distyrylbenzene-aldehydes: identification of proteins in water. Supporting Information Electronic Supplementary Material (ESI) for Analyst. This journal is The Royal Society of Chemistry 2015 Distyrylbenzene-aldehydes: identification of proteins in water Jan Kumpf, Jan Freudenberg and Uwe

More information

Maksim A. Kolosov*, Olesia G. Kulyk, Elena G. Shvets, Valeriy D. Orlov

Maksim A. Kolosov*, Olesia G. Kulyk, Elena G. Shvets, Valeriy D. Orlov 1 Synthesis of 5-cinnamoyl-3,4-dihydropyrimidine-2(1H)-ones Supplementary Information Maksim A. Kolosov*, lesia G. Kulyk, Elena G. Shvets, Valeriy D. rlov Department of organic chemistry, V.N.Karazin Kharkiv

More information

Influence of anellation in N-heterocyclic carbenes: Detection of novel quinoxalineanellated NHC by trapping as transition metal complexes

Influence of anellation in N-heterocyclic carbenes: Detection of novel quinoxalineanellated NHC by trapping as transition metal complexes Influence of anellation in N-heterocyclic carbenes: Detection of novel quinoxalineanellated NHC by trapping as transition metal complexes Shanmuganathan Saravanakumar, a Markus K. Kindermann, a Joachim

More information

Supporting information. Enantioselective synthesis of 2-methyl indoline by palladium catalysed asymmetric C(sp 3 )-H activation/cyclisation.

Supporting information. Enantioselective synthesis of 2-methyl indoline by palladium catalysed asymmetric C(sp 3 )-H activation/cyclisation. Supporting information Enantioselective synthesis of 2-methyl indoline by palladium catalysed asymmetric C(sp 3 )-H activation/cyclisation Saithalavi Anas, Alex Cordi and Henri B. Kagan * Institut de Chimie

More information

Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry Supplementary data

Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry Supplementary data Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2012 Supplementary data Cu-catalyzed in situ generation of thiol using xanthate as thiol

More information

(2) After dissolving a solid in a solvent at high temperature, the solution is not filtered.

(2) After dissolving a solid in a solvent at high temperature, the solution is not filtered. Name Key 216 W13-Exam No. 1 Page 2 I. (10 points) The goal of recrystallization is to obtain purified material with a maximized recovery. For each of the following cases, indicate as to which of the two

More information

Supporting information

Supporting information Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C. This journal is The Royal Society of Chemistry 2015 Supporting information Porosity induced emission: exploring color-controllable

More information

SUPPLEMENTARY INFORMATION

SUPPLEMENTARY INFORMATION doi:10.1038/nature24451 Chemical synthesis of USP7 compounds General 1 H, 13 C and 19 F nuclear magnetic resonance (NMR) spectra were obtained on either Bruker or Varian spectrometers at 300 or 400 MHz,

More information

Anion binding vs. sulfonamide deprotonation in functionalised ureas

Anion binding vs. sulfonamide deprotonation in functionalised ureas S Anion binding vs. sulfonamide deprotonation in functionalised ureas Claudia Caltagirone, Gareth W. Bates, Philip A. Gale* and Mark E. Light Supplementary information Experimental Section General remarks:

More information

Electronic Supporting Information

Electronic Supporting Information Electronic Supporting Information Reactions of Tp(NH=CPh 2 )(PPh 3 )Ru Cl with HC CPh in the presence of H 2 O: Insertion/Hydration Products Chih-Jen Cheng, a Hung-Chun Tong, a Yih-Hsing Lo,* b Po-Yo Wang,

More information

Supporting Information. for. Angew. Chem. Int. Ed. Z Wiley-VCH 2003

Supporting Information. for. Angew. Chem. Int. Ed. Z Wiley-VCH 2003 Supporting Information for Angew. Chem. Int. Ed. Z50567 Wiley-VCH 2003 69451 Weinheim, Germany Metallacarborane-Based Nanostructures: A Carbon-Wired Planar Octagon** Haijun Yao, Michal Sabat, and Russell

More information

Supporting information

Supporting information Supporting information Access to Aminated Saturated Oxygen Heterocycles via Copper-Catalyzed Aminooxygenation of Alkenes Jian Xie, Yue-Wei Wang, Lian-Wen Qi,* and Bo Zhang* State Key Laboratory of Natural

More information

Asymmetric Organocatalytic Strecker-Type Reactions of Aliphatic N,N- Dialkylhydrazones

Asymmetric Organocatalytic Strecker-Type Reactions of Aliphatic N,N- Dialkylhydrazones Asymmetric Organocatalytic Strecker-Type Reactions of Aliphatic N,N- Dialkylhydrazones Aurora Martínez-Muñoz, David Monge,* Eloísa Martín-Zamora, Eugenia Marqués-López, Eleuterio Álvarez, Rosario Fernández,*

More information

Working with Hazardous Chemicals

Working with Hazardous Chemicals A Publication of Reliable Methods for the Preparation of Organic Compounds Working with Hazardous Chemicals The procedures in Organic Syntheses are intended for use only by persons with proper training

More information

Nucleophilicities and Lewis basicities of imidazoles, benzimidazoles, and benzotriazoles

Nucleophilicities and Lewis basicities of imidazoles, benzimidazoles, and benzotriazoles This journal is The Royal Society of Chemistry 21 Electronic Supporting Information (ESI) Nucleophilicities and Lewis basicities of imidazoles, benzimidazoles, and benzotriazoles Mahiuddin Baidya, Fran

More information

Continuous flow iodination using an automated computer-vision controlled liquid-liquid extraction system [Supporting Information]

Continuous flow iodination using an automated computer-vision controlled liquid-liquid extraction system [Supporting Information] Continuous flow iodination using an automated computer-vision controlled liquid-liquid extraction system [Supporting Information] Matthew O Brien*, Dennis A. Cooper and Jonathan Dolan. Lennard-Jones Building,

More information

A TPE-oxazoline molecular switch with tunable multi-emission in. both solution and solid state

A TPE-oxazoline molecular switch with tunable multi-emission in. both solution and solid state Electronic Supplementary Information (ESI) A TPE-oxazoline molecular switch with tunable multi-emission in both solution and solid state Qingkai Qi a, Xiaofeng Fang b, Yifei Liu* b, Peng Zhou b, Yumo Zhang

More information

Supplementary Information

Supplementary Information Supplementary Information (1) Synthesis and Characterization Figure S1. 1 H-NMR of 3 (400 MHz; CDCl3; rt). Figure S2. 13 C-NMR of 3 (100 MHz; CDCl3; rt). S2 8000 7500 7000 6500 6000 5500 5000 4500 4000

More information

3-Bromomethyl pyridine

3-Bromomethyl pyridine M 3 L 2 metallo-cryptophanes: [2]catenane and simple cages James J. Henkelis, Tanya K. Ronson, Lindsay P. Harding and Michaele J. Hardie Supplementary Material Synthesis Chemicals were obtained from commercial

More information

Table of Contents 1. General procedure for the chiral phosphoric acid catalyzed asymmetric reductive amination using benzothiazoline

Table of Contents 1. General procedure for the chiral phosphoric acid catalyzed asymmetric reductive amination using benzothiazoline Enantioselective Organocatalytic Reductive Amination of Aliphatic Ketones by Benzothiazoline as Hydrogen Donor Kodai Saito, Takahiko Akiyama* Department of Chemistry, Faculty of Science, Gakushuin University,

More information

A thermally-stable enzyme detection assay that amplifies signal autonomously in water without assistance from biological reagents

A thermally-stable enzyme detection assay that amplifies signal autonomously in water without assistance from biological reagents A thermally-stable enzyme detection assay that amplifies signal autonomously in water without assistance from biological reagents Table of Contents Kimy Yeung, Kyle M. Schmid, and Scott T. Phillips* Department

More information

A "turn-on" coumarin-based fluorescent sensor with high selectivity for mercury ions in aqueous media

A turn-on coumarin-based fluorescent sensor with high selectivity for mercury ions in aqueous media A "turn-on" coumarin-based fluorescent sensor with high selectivity for mercury ions in aqueous media Styliani Voutsadaki, George K. Tsikalas, Emmanuel Klontzas, George E. Froudakis, and Haralambos E.

More information

Supporting Information

Supporting Information Organocatalytic Aerobic Oxidation of Benzylic sp 3 C-H Bonds of Ethers and Alkylarenes Promoted by a Recyclable TEMPO Catalyst Zhiguang Zhang, Yuan Gao, Yuan Liu, Jianjun Li, Hexin Xie, Hao Li,*, and Wei

More information

Supporting Information for Exploration of C H and N H-bond functionalization towards 1-(1,2-diarylindol-3-yl)- tetrahydroisoquinolines

Supporting Information for Exploration of C H and N H-bond functionalization towards 1-(1,2-diarylindol-3-yl)- tetrahydroisoquinolines Supporting Information for Exploration of C H and N H-bond functionalization towards 1-(1,2-diarylindol-3-yl)- tetrahydroisoquinolines Michael Ghobrial, Marko D. Mihovilovic and Michael Schnürch* Address:

More information

Experiment : Reduction of Ethyl Acetoacetate

Experiment : Reduction of Ethyl Acetoacetate Experiment 7-2007: eduction of Ethyl Acetoacetate EXPEIMENT 7: eduction of Carbonyl Compounds: Achiral and Chiral eduction elevant sections in the text: Fox & Whitesell, 3 rd Ed. Chapter 12, pg.572-584.

More information

Supporting Information. for. Angew. Chem. Int. Ed. Z Wiley-VCH 2004

Supporting Information. for. Angew. Chem. Int. Ed. Z Wiley-VCH 2004 Supporting Information for Angew. Chem. Int. Ed. Z54084 Wiley-VCH 2004 69451 Weinheim, Germany A LiCl-Mediated Br/Mg-Exchange Reaction for the Preparation of Functionalized Aryl and Heteroaryl Magnesium

More information

Electronic Supplementary Information. A novel generation of hybrid photochromic. through fine-tuning of surface chemistry

Electronic Supplementary Information. A novel generation of hybrid photochromic. through fine-tuning of surface chemistry Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2017 Electronic Supplementary Information A novel generation of hybrid photochromic vinylidene-naphthofuran

More information

Halogen bonded dimers and ribbons from the self-assembly of 3-halobenzophenones Patricia A. A. M. Vaz, João Rocha, Artur M. S. Silva and Samuel Guieu

Halogen bonded dimers and ribbons from the self-assembly of 3-halobenzophenones Patricia A. A. M. Vaz, João Rocha, Artur M. S. Silva and Samuel Guieu Electronic Supplementary Material (ES) for CrystEngComm. This journal is The Royal Society of Chemistry 27 Halogen bonded dimers and ribbons from the self-assembly of -halobenzophenones Patricia A. A.

More information

The Grignard Reaction: Synthesis of 1,2-diphenyl-1,2-propanediol via a Diastereoselective Reaction.

The Grignard Reaction: Synthesis of 1,2-diphenyl-1,2-propanediol via a Diastereoselective Reaction. EXPERIMENT 2 The Grignard Reaction: Synthesis of 1,2-diphenyl-1,2-propanediol via a Diastereoselective Reaction. Relevant sections in the text: Fox & Whitesell, 3 rd Ed. pg. 400-404, 615-618 General Concepts

More information

Supplementary Information. Mapping the Transmission Function of Single-Molecule Junctions

Supplementary Information. Mapping the Transmission Function of Single-Molecule Junctions upplementary Information Mapping the Transmission Function of ingle-molecule Junctions Brian Capozzi 1, Jonathan Z. Low 2, Jianlong Xia 3, Zhen-Fei Liu 4, Jeffrey B. Neaton 5,6, Luis M. Campos 2, Latha

More information

Electronic Supporting Information

Electronic Supporting Information Electronic Supplementary Material (ESI) for New Journal of Chemistry. This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2014 Electronic Supporting Information

More information

Supporting Information for. Singlet oxygen initiated cascade transformation of a simple difuran into the key ABC motif of the pectenotoxins

Supporting Information for. Singlet oxygen initiated cascade transformation of a simple difuran into the key ABC motif of the pectenotoxins Supporting Information for Singlet oxygen initiated cascade transformation of a simple difuran into the key ABC motif of the pectenotoxins Georgios Vassilikogiannakis, * Ioanna Alexopoulou, Maria Tofi

More information

Supporting Information

Supporting Information Supporting Information Wiley-VCH 2006 69451 Weinheim, Germany Engineering Polymeric Chiral Catalyst Using Hydrogen Bonding and Coordination Interactions Lei Shi, 1,2 Xingwang Wang, 1 Christian A. Sandoval,

More information

Highly Efficient Chemoselective N-TBS Protection of Anilines under Exceptional Mild Conditions in the Eco-Friendly Solvent 2- Methyltetrahydrofuran.

Highly Efficient Chemoselective N-TBS Protection of Anilines under Exceptional Mild Conditions in the Eco-Friendly Solvent 2- Methyltetrahydrofuran. Supporting Information For Highly Efficient Chemoselective N-TBS Protection of Anilines under Exceptional Mild Conditions in the Eco-Friendly Solvent 2- Methyltetrahydrofuran. Vittorio Pace, *a,b Andrés

More information

Photochemical studies of (η 5 -C 5 H 5 )Ru(PPh 3 ) 2 Cl and (η 5 -C 5 H 5 )Ru(PPh 3 ) 2 Me: formation of Si-H and C-H bond activation products.

Photochemical studies of (η 5 -C 5 H 5 )Ru(PPh 3 ) 2 Cl and (η 5 -C 5 H 5 )Ru(PPh 3 ) 2 Me: formation of Si-H and C-H bond activation products. Photochemical studies of (η 5 -C 5 H 5 )( ) 2 Cl and (η 5 -C 5 H 5 )( ) 2 : formation of Si-nd C-ond activation products. Johnathan L. Clark and Simon B. Duckett* 1. Experimental Materials. The deuterated

More information

Total Synthesis of (±)-Gracilioether F

Total Synthesis of (±)-Gracilioether F Total Synthesis of (±)-Gracilioether F Xin-Yue Shen, Xiao-Shui Peng,, Henry N. C. Wong*, Department of Chemistry, and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong, Shatin,

More information

ph-responsive Quantum Dots (RQDs) that Combine a Fluorescent Nanoparticle with a ph-sensitive Dye

ph-responsive Quantum Dots (RQDs) that Combine a Fluorescent Nanoparticle with a ph-sensitive Dye Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics. This journal is the Owner Societies 2014 ph-responsive Quantum Dots (RQDs) that Combine a Fluorescent Nanoparticle with

More information

Electronic Supplementary Information

Electronic Supplementary Information S1 Electronic Supplementary Information Direct Aerobic Oxidation of 2-Benzylpyridines in a Gas- Liquid Continuous-Flow Regime Using Propylene Carbonate as Solvent Bartholomäus Pieber and C. Oliver Kappe*

More information

Electronic Supplementary Material

Electronic Supplementary Material Electronic Supplementary Material Pharmacological evaluation of synthetic cannabinoids identified as constituents of spice Cornelius Hess 1, Clara T. Schoeder 2,3, Thanigaimalai Pillaiyar 2, Burkhard Madea

More information

Supporting Information

Supporting Information Supporting Information A Short and Flexible Route to Tetrahydropyran-4-ones via Conjugated Nitrile xides Cycloaddition and xa-michael Cyclization: A Concise Diastereoselective Total Synthesis of ( )-Diospongin

More information

Supporting Information

Supporting Information Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2013 ph-controlled Reversible Formation of a Supramolecular Hyperbranched Polymer Showing Fluorescence Switching Bingran

More information

A supramolecular approach for fabrication of photo- responsive block-controllable supramolecular polymers

A supramolecular approach for fabrication of photo- responsive block-controllable supramolecular polymers Electronic Supplementary Material (ESI) for Polymer Chemistry. This journal is The Royal Society of Chemistry 2014 Supporting Information A supramolecular approach for fabrication of photo- responsive

More information

Catalytic Conjugate Additions of Nitrogen, Phosphorus, and Carbon-containing Nucleophiles. by Amphoteric Vanadyl Triflate

Catalytic Conjugate Additions of Nitrogen, Phosphorus, and Carbon-containing Nucleophiles. by Amphoteric Vanadyl Triflate Catalytic Conjugate Additions of Nitrogen, Phosphorus, and Carbon-containing Nucleophiles by Amphoteric Vanadyl Triflate S1 Yow-Dzer Lin, Jun-Qi Kao, and Chien-Tien Chen* Department of Chemistry, National

More information

Stoichiometric Reductions of Alkyl-Substituted Ketones and Aldehydes to Borinic Esters Lauren E. Longobardi, Connie Tang, and Douglas W.

Stoichiometric Reductions of Alkyl-Substituted Ketones and Aldehydes to Borinic Esters Lauren E. Longobardi, Connie Tang, and Douglas W. Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2014 Supplementary Data for: Stoichiometric Reductions of Alkyl-Substituted Ketones and Aldehydes

More information

Supporting Information

Supporting Information Supporting Information One Pot Synthesis of 1,3- Bis(phosphinomethyl)arene PCP/PNP Pincer Ligands and Their Nickel Complexes Wei-Chun Shih and Oleg V. Ozerov* Department of Chemistry, Texas A&M University,

More information

5.37 Introduction to Organic Synthesis Laboratory

5.37 Introduction to Organic Synthesis Laboratory MIT pencourseware http://ocw.mit.edu 5.37 Introduction to rganic Synthesis Laboratory Spring 2009 For information about citing these materials or our Terms of Use, visit: http://ocw.mit.edu/terms. URIECA

More information

Benzene-1,3,5-tricarboxamide n-alkyl ester and carboxylic acid derivatives: Tuneable structural, morphological and thermal properties

Benzene-1,3,5-tricarboxamide n-alkyl ester and carboxylic acid derivatives: Tuneable structural, morphological and thermal properties Electronic Supplementary Material (ESI) for CrystEngComm. This journal is The Royal Society of Chemistry 2017 Benzene-1,3,5-tricarboxamide n-alkyl ester and carboxylic acid derivatives: Tuneable structural,

More information

Tsuji Trost N-Allylation with Allylic Acetates by Using a Cellulose Palladium Catalyst

Tsuji Trost N-Allylation with Allylic Acetates by Using a Cellulose Palladium Catalyst University of Nebraska - Lincoln DigitalCommons@University of Nebraska - Lincoln U.S. Environmental Protection Agency Papers U.S. Environmental Protection Agency 2012 Tsuji Trost N-Allylation with Allylic

More information

Pyrimidine Acyclo-C-Nucleosides by Ring Transformations of 2- Formyl-L-arabinal

Pyrimidine Acyclo-C-Nucleosides by Ring Transformations of 2- Formyl-L-arabinal Molecules 005, 0, 837-84 molecules ISS 40-3049 http://www.mdpi.org Pyrimidine Acyclo-C-ucleosides by Ring Transformations of - Formyl-L-arabinal Ahmed Bari, Holger Feist, Manfred Michalik and Klaus Peseke,*

More information

Enantioselective Synthesis of Hindered Cyclic Dialkyl Ethers via Catalytic Oxa- Michael/Michael Desymmetrization.

Enantioselective Synthesis of Hindered Cyclic Dialkyl Ethers via Catalytic Oxa- Michael/Michael Desymmetrization. SUPPRTING INFRMATIN Enantioselective Synthesis of indered Cyclic Dialkyl Ethers via Catalytic xa- Michael/Michael Desymmetrization Michael T. Corbett and Jeffrey S. Johnson Department of Chemistry, University

More information

Asymmetric Hydrovinylation of Unactivated Linear 1,3-Dienes

Asymmetric Hydrovinylation of Unactivated Linear 1,3-Dienes Asymmetric Hydrovinylation of Unactivated Linear 1,3-Dienes Rakesh K. Sharma and T. V. RajanBabu* Department of Chemistry, The Ohio State University, 100 W. 18 th Avenue, Columbus, OH 43210, USA SUPPORTING

More information

Electronic Supplementary Information for Catalytic Asymmetric Hydrophosphonylation of Ynones

Electronic Supplementary Information for Catalytic Asymmetric Hydrophosphonylation of Ynones Electronic Supplementary Information for Catalytic Asymmetric Hydrophosphonylation of Ynones Daisuke Uraguchi, Takaki Ito, Shinji Nakamura, and Takashi oi* Department of Applied Chemistry, Graduate School

More information

Supporting information

Supporting information Electronic Supplementary Material (ESI) for New Journal of Chemistry. This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2015 Supporting information Influence

More information

Enantioselective, intermolecular [2+2] photocycloaddition reactions of 3-acetoxyquinolone: Total synthesis of ( )- pinolinone

Enantioselective, intermolecular [2+2] photocycloaddition reactions of 3-acetoxyquinolone: Total synthesis of ( )- pinolinone Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2014 Enantioselective, intermolecular [2+2] photocycloaddition reactions of 3-acetoxyquinolone: Total

More information

Chapter IV. Secondary Ammonium Salts

Chapter IV. Secondary Ammonium Salts Chapter IV Secondary Ammonium Salts IV.1. Introduction Several secondary ammonium salts with hexafluorophosphate counterions were synthesized. To study the complexation behavior of these salts in solution

More information

Issue in Honor of Prof. Rainer Beckert ARKIVOC 2012 (iii) 5-19

Issue in Honor of Prof. Rainer Beckert ARKIVOC 2012 (iii) 5-19 Issue in Honor of Prof. Rainer Beckert ARKIVC 212 (iii) 5-19 Lewis acid-catalyzed Diels-Alder reaction of 2-cyclopentenones with Danishefsky s diene: double bond isomerization of tetrahydro-1hindene-1,5(7ah)-diones,

More information

Rational design of a ratiometric fluorescent probe with a large emission shift for the facile detection of Hg 2+

Rational design of a ratiometric fluorescent probe with a large emission shift for the facile detection of Hg 2+ Rational design of a ratiometric fluorescent probe with a large emission shift for the facile detection of Hg 2+ Weimin Xuan, a Chen Chen, b Yanting Cao, a Wenhan He, a Wei Jiang, a Kejian Li, b* and Wei

More information

Supporting Information

Supporting Information Supporting Information Phosphane-free Suzuki Miyaura Coupling of Aryl Imidazolesulfonates with Arylboronic Acids and Potassium Aryltrifluoroborates under Aqueous Conditions José Francisco Cívicos, Mohammad

More information

Supplementary Information

Supplementary Information Catalytically Efficient Palladium anoparticles Stabilized by Click rrocenyl Dendrimers Cátia rnelas, Lionel Salmon, Jaime Ruiz Aranzaes, Didier Astruc Supplementary Information Cyclic Voltammetry (CV),

More information

A selenium-contained aggregation-induced turn-on fluorescent probe for hydrogen peroxide

A selenium-contained aggregation-induced turn-on fluorescent probe for hydrogen peroxide Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2014 Electronic Supplementary Information (ESI) A selenium-contained aggregation-induced

More information

Selective Metalations of 1,4-Dithiins and Condensed Analogs using TMP-Magnesium and -Zinc Bases

Selective Metalations of 1,4-Dithiins and Condensed Analogs using TMP-Magnesium and -Zinc Bases Selective Metalations of,4-dithiins and Condensed Analogs using TMP-Magnesium and -Zinc Bases Alicia Castelló-Micó, a Julia Nafe, a Kosuke Higashida, a Konstantin Karaghiosoff, a Marc Gingras, b Paul Knochel

More information

Synthesis, characterization and molecular recognition of bis-platinum terpyridine dimer. Supporting information

Synthesis, characterization and molecular recognition of bis-platinum terpyridine dimer. Supporting information This journal is (c) The Royal Society of Chemistry 008 Synthesis, characterization and molecular recognition of bis-platinum terpyridine dimer Robert Trokowski, Shigehisa Akine, Tatsuya abeshima Graduate

More information