Supporting Information

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1 Supporting Information Wiley-VCH Weinheim, Germany Asymmetric Cascade Reaction to Allylic Sulfonamides from Allylic Alcohols by Palladium(II)/Base-Catalyzed Rearrangement of Allylic Carbamates** Johannes Moritz Bauer, Wolfgang Frey, and RenØ Peters* ange_ _sm_miscellaneous_information.pdf

2 Table of Contents General Remarks... 3 General Procedures... 4 Synthesis of Allylic Alcohols (4)... 7 Synthesis of N-Sulfonyl Protected Allylic Carbamates (1, 5, 8) Synthesis of N-Sulfonyl Protected Allylic Amines (2, 6, 9) Synthesis of Allylic Amines (7) Mechanistic Investigations NMR Spectra of New Compounds HPLC Spectra of Compounds (2, 6, 7) References S2

3 General Remarks All reactions were performed in oven-dried glassware (oven temperature at 150 C) and unless otherwise indicated under a positive pressure of nitrogen (about 0.2 bar). Liquids were added via syringe and solids were added neat against a nitrogen flow. Solvents were removed by rotary evaporation at a heating bath temperature of 40 C and mbar pressure. Non-volatile compounds were dried in vacuo at ca. 0.1 mbar. Absolution of dichloromethane and THF used for reactions was achieved by a solvent purification system. Dimethylformamide (99.8%) and chloroform were stored in crown-capped bottles over 4Å molecular sieves and used as purchased. For work-up procedures and flash chromatography, distilled technical grade solvents were used. n-hexane and ipropanol (HPLC-quality) were used as purchased. [PPFOP-Cl]2[1] was prepared according to literature procedures. All other laboratory chemicals were used without purification unless otherwise indicated. Yields refer to purified compounds and are calculated in mol% of the used starting material. Except otherwise indicated, reactions were magnetically stirred and monitored by NMR-spectroscopy or thin layer chromatography (TLC) using silica gel plates (silica gel 60 F254). Visualization occurred by fluorescence quenching under UV light and/or staining with KMnO4/NaOH. Purification by flashchromatography was performed on silica gel mm using a forced flow of eluent at moderate pressure applied with a hand pump. NMR-spectra were recorded at 21 C at 500, 300 or 250 MHz (1H) and 125 or 75 MHz (13C). Chemical shifts δ are referred in terms of ppm and coupling constants J are given in Hz. Abbreviations for multiplicities are as follows: s (singulet), d (duplet), t (triplet), q (quartet), m (multiplet), p (pentet), hex (sextet), hep (heptet) and b (broad signal). IRspectra were recorded by the analytical service of the Universität Stuttgart on a FT-IR spectrometer with ATR unit and the signals are given by wavenumbers (cm 1). Melting points were measured in open glass capillaries and are uncorrected. Optical rotation was measured at the sodium D line in a 100 mm path cell length. The ee values were determined by chiral stationary phase HPLC. Racemic reference samples were prepared according to literature.[2] Mass spectra were obtained from the analytical service of the Universität Stuttgart. Ionization methods are stated in parenthesis. Single crystal X-ray analysis was performed by Dr. Wolfgang Frey (Universität Stuttgart). S3

4 General Procedures General Procedure for the Synthesis of N-Sulfonyl Protected Allylic Carbamates (GP1) Following a literature procedure,[3] to a solution of the allylic alcohol (4, 1 equiv.) in CH2Cl2 (1 ml per 1 mmol) at 0 C was added the corresponding sulfonyl isocyanate (1 equiv.) dropwise. The resulting mixture was then stirred at room temperature for 2 h. Subsequently 1M aqueous HCl was added and the layers were separated. The aqueous layer was extracted twice with CH2Cl2, the combined organic layers were dried over Na2SO4, concentrated to dryness and the N-sulfonyl protected allylic carbamate was then purified by silica gel chromatoghraphy. General Procedure for the Synthesis of N-Sulfonyl Protected Allylic Carbamates via CDI-Activation (GP2) According to a literature procedure, [4] to a suspension of CDI (1,1 -carbonyldiimidazol) (1.2 equiv.) in CH2Cl2 (1.25 ml per 1 mmol) was added the corresponding allylic alcohol (4, 1.0 equiv.) neat or as solution in CH2Cl2 (1.50 ml per 1 mmol) dropwise at room temperature. After stirring at room temperature for 4 h, the mixture was diluted with water and extracted twice with CH2Cl2. The combined organic layers were washed twice with water and dried over Na2SO4. Removal of solvent under reduced pressure yielded the activated alcohol, which was directly used for the next step without further purification. The activated alcohol (1.0 equiv.) was dissolved in DMF (1.6 ml per 1 mmol). To this solution was added DMAP (N,N-dimethylpyridin-4-amine) (1.0 equiv.), Hünig s base (ipr2net) (1.0 equiv.) and the corresponding sulfonamide (1.0 equiv.). The flask was closed by a cap and the mixture was stirred for 14 h at 80 C. Afterwards the mixture was diluted with CH2Cl2 and washed with three times with 1M aqueous HCl. The aqueous layer was extracted twice with CH2Cl2, the combined organic layers were dried over Na2SO4 and the solvent was removed under reduced pressure. Purification by column chromatography yielded the N-sulfonyl protected carbamate. S4

5 General Procedure for the Activation of [PPFOP-Cl]2 (GP3) [PPFOP-Cl]2 (1 equiv.) and the corresponding silver salt (2 equiv.) were suspended in CH2Cl2 (1 ml per 10 mg [PPFOP-Cl]2) and the mixture was ultrasonificated for 10 min. Afterwards the suspension was stirred for 14 h at room temperature. After the activation was complete the mixture was filtered through CaH2/celite (1:1) and the solvent was removed by a stream of nitrogen. A stock solution in CH2Cl2 was subsequently prepared. General Procedure for the Decarboxylative Rearrangement of NSulfonyl Protected Carbamates (GP4) The corresponding N-sulfonyl protected carbamate (1.00 equiv.) and proton sponge (1,8-bis(N,Ndimethylamino)naphthalene) (1.0 to 0.1 equiv.) were charged to a screw-cap vial. Vacuum was then applied and the vial was subsequently flushed with nitrogen (3 times repeated). The activated catalyst (prepared from 5 to 1 mol% [PPFOP-Cl]2, as described in GP3) was added as a stock solution in CH2Cl2 (typically 150 μl per 100 μmol). The vial was closed and the mixture was stirred for the indicated time at the indicated temperature. Afterwards the mixture was diluted with CH2Cl2 and washed with aqueous 1M HCl. The aqueous layer was extracted twice with CH2Cl2, the combined organic layers were dried over Na2SO4 and the solvent was removed under reduced pressure. To determine conversion, regioselectivity and yield of the reaction by 1H-NMR, mesitylene (10 μl per 100 μmol) was added to the crude product as an internal standard followed by CDCl3 (1 ml) (after cooling to room temperature). The crude product was afterwards directly used for silica gel chromatography to isolate the corresponding N-sulfonyl protected allylic amine. The purified samples were used to determine the ee value by HPLC. S5

6 General Tandem-Procedure for the Catalytic Asymmetric Synthesis of N-Tosyl Protected Allylic Amines (GP5) A dry screw-cap vial was charged under air with [PPFOP-Cl]2 (1 mol%), proton sponge (1,8-bis(N,Ndimethylamino)naphthaline) (20 mol%), the corresponding allylic alcohol (4, 1.00 equiv.) and ptosylisocyanate (1.00 equiv.). Subsequently CHCl3 (100 μl per 68 µmol allylic alcohol) was added. The vial was closed and the mixture was stirred for 24 h at 80 C. The solution was then diluted with CH2Cl2 and washed with aqueous 1M HCl. The layers were separated and the aqueous phase was extracted twice with CH2Cl2. The combined organic layers were dried over Na2SO4 and the solvent removed under reduced pressure. After determination of the regioselectivity as described in GP4 via 1 H-NMR, the product 2 was isolated by silica gel chromatography. The purified samples were used to determine the ee value by HPLC. S6

7 Synthesis of Allylic Alcohols (4) Commercially available: The following allylic alcohols used in these investigations are commercially available in sufficiently high isomerical purity: trans-hex-2-en-1-ol (4a), cis-hex-2-en-1-ol ((Z)-4a), trans-pent-2-en-1-ol (4b), trans-oct-2-en-1-ol (4d). Via HWE-reaction: The following alcohols were prepared according to a literature procedure utilizing a highly (E)selective version of the Horner-Wadsworth-Emmons reaction (HWE-reaction),[5] followed by reduction with DIBAL-H: Trans-5-phenylpent-2-en-1-ol (4e),[6] trans-5-methylhex-2-en-1-ol (4j), trans-4-methylpent-2-en-1-ol (4i),[7] trans-but-2-en-1-ol (4c) (ethyl crotonate is commercially available in sufficiently high isomerical purity). Representative Procedure for HWE and DIBAL-H-Reduction: trans-5-phenylpent-2- en-1-ol (4e) To a solution of trimethylphosphonoacetate (1.00 equiv., 1.40 mmol, mg, 200 µl) in THF (10 ml) was added MeMgBr (0.86 equiv., 1.20 mmol, 400 µl of a 3M solution in Et2O) dropwise at room temperature. This mixture was stirred at room temperature for additional 20 min, then 3phenylpropionaldehyde (0.97 equiv., 1.32 mmol, mg, 180 µl) was added in one portion and the S7

8 solution was stirred at room temperature for another 1 h. Subsequently saturated aqueous NH4Cl (6.3 ml) was added and the mixture was extracted with Et2O (2 times 20 ml). The combined organic phases were dried over Na2SO4 and the solvent was removed under reduced pressure (E/Z ratio of the crude product: 97:3). Purification by silica gel chromatography (petrol ether/ethyl acetate = 10:1) yielded the intermediate ester as a colourless oil (0.58 mmol, mg, 48%, E/Z > 99:1). C12H14O2, MW: g/mol. 1H-NMR (CDCl3, 300 MHz): δ = (m, 2 H), (m, 3 H), 7.00 (dt, J = 15.6, 6.8, 1 H), 5.85 (dt, J = 15.6, 1.5, 1 H), 3.72 (s, 3 H), (m, 2 H), (m, 2 H). The other analytical data are in accordance with the literature.[8] To a solution of the ester (1.00 equiv., 2.09 mmol, mg) in CH2Cl2 (5 ml) at 78 C was added DIBAL-H (2.63 equiv., 5.50 mmol, 5 ml of a 1.1M solution in cyclohexane) in one portion. After stirring for 15 min at this temperature, the solution was slowly warmed to room temperature and stirred for 1.5 h. Subsequently the mixture was cooled again to 78 C and aqueous hydrochloric acid (1M, 28 ml) was added until all solid had dissolved. The mixture was extracted with CH2Cl2 (2 times 20 ml), the combined organic phases were dried over MgSO4 and the solvent removed under reduced pressure. Purification by silica gel chromatography (petrol ether/ethyl acetate = 5:1) yielded the alcohol 4e as a colorless oil (2.03 mmol, mg, 97%, E/Z > 99:1). C11H14O, MW: g/mol. 1H-NMR (CDCl3, 300 MHz): δ = (m, 2 H), (m, 3 H), (m, 2 H), 4.09 (d, J = 5.0, 2 H), (m, 2 H), (m, 2 H), 1.28 (bs, 1 H). The other analytical data are in accordance with the literature.[6] Via LiAlH4-reduction and protection: The following alcohols were prepared according to a literature procedure utilizing a LiAlH4reduction,[9] followed by subsequent alcohol protection: (E)-4-((tert-butyldimethylsilyl)oxy)but-2-en-1-ol (4g),[10] (E)-4-(benzyloxy)but-2-en-1-ol (4h).[11] Procedure for LiAlH4-reduction: (E)-2-Butene-1,4-diol Following a literature procedure,[9] a suspension of lithium aluminum hydride (1.20 equiv., 17.4 mmol, mg) in THF (50 ml) was cooled to 0 C. A solution of butyne-1,4-diol (1.00 equiv., 14.5 mmol, 1.25 g) in THF (13 ml) was added with vigorous stirring. The reaction was stirred for 20 min at 0 C before it was warmed to room temperature and allowed to stir for 12 h. Subsequently the mixture was S8

9 cooled again to 0 C and celite (300 mg) was added. Then the mixture was hydrolyzed by the addition of saturated aqueous (NH4)2SO4 (1.6 ml), filtered through celite and the filter cake was washed thoroughly with Et2O and CH2Cl2. Removal of solvent under reduced pressure and Kugelrohr distillation (13 mbar, 145 C) yielded (E)-2-butene-1,4-diol as a colorless oil (9.6 mmol, mg, 67%). C4H8O2, MW: g/mol. 1H-NMR (CDCl3, 300 MHz): δ = (m, 2 H), (m, 4 H), 1.58 (bs, 2 H). The other analytical data are in accordance with the literature.[9] (E)-4-((tert-Butyldimethylsilyl)oxy)but-2-en-1-ol (4g) Following a literature procedure,[10] to a solution of (E)-2-butene-1,4-diol (1.00 equiv., 9.6 mmol, mg) in THF (35 ml) at 0 C was added NaH (1.01 equiv., 9.7 mmol, mg, 60% in oil) and the mixture was stirred for 1 h at room temperature. A solution of TBS-Cl (1.02 equiv., 9.9 mmol, 1.49 g) in THF (10 ml) was added dropwise and the mixture was stirred for 3 h at room temperature. Subsequently the reaction was quenched by the addition of saturated aqueous NH4Cl (25 ml), the mixture was extracted with Et2O (3 times 60 ml) and the combined organic layers dried over MgSO4. Removal of solvent under reduced pressure and purification by silica gel chromatography (petrol ether/ethyl acetate = 9:1) yielded the alcohol 4g as a colorless oil (3.46 mmol, mg, 36%). C10H22O2Si, MW: g/mol. 1H-NMR (CDCl3, 300 MHz): δ = (m, 2 H), (m, 4 H), 1.54 (bs, 1 H), 0.91 (s, 9 H), 0.07 (s, 6 H). The other analytical data are in accordance with the literature.[10] (E)-4-(Benzyloxy)but-2-en-1-ol (4h) Following a literature procedure,[11] to a solution of (E)-2-butene-1,4-diol (1.97 equiv., mmol, 1.00 g) in THF (6 ml) at 0 C was added NaH (1.08 equiv., 6.25 mmol, mg, 60% in oil) and the mixture was stirred for 1 h at 0 C. Benzyl bromide (1.00 equiv., 5.77 mmol, 987 mg, 700 µl) was then added dropwise and the mixture was stirred for 1 h at 75 C. Subsequently the mixture was cooled again to room temperature, quenched by the addition of saturated aqueous NH4Cl (25 ml) and extracted with CH2Cl2 (3 times 30 ml). The combined organic layers were dried over MgSO4 and the solvent was removed under reduced pressure. Purification by silica gel chromatography (petrol ether/ethyl acetate = 4:1) yielded the alcohol 4h as a colorless oil (3.09 mmol, mg, 54%). S9

10 C11H14O2, MW: g/mol. 1H-NMR (CDCl3, 300 MHz): δ = (m, 5 H), (m, 2 H), 4.53 (s, 2 H), (m, 2 H), (m, 2 H), 1.41 (t, J = 5.9, 1 H). The other analytical data are in accordance with the literature.[12] Via cross metathesis and NaBH4-reduction: The following alcohol was prepared according to literature procedures utilizing a cross metathesis[13] followed by a selective NaBH4-reduction[14]: (E)-Methyl 6-oxohex-4-enoate (4f) According to a literature procedure,[13] to a solution of pent-4-enoic acid (1.00 equiv., 9.99 mmol, 1.00 g) in MeOH (17 ml) was added concentrated H2SO4 (0.1 ml) and the mixture was refluxed for 3 h. Subsequently the mixture was cooled again to room temperature, water (25 ml) was added and the resulting mixture was extracted with Et2O (3 times 20 ml). The combined organic layers were dried over MgSO4 and the solvent removed under reduced pressure (40 C, till 200 mbar). Purification by Kugelrohr distillation (700 mbar, 130 C) yielded the ester as a colorless oil (5.76 mmol, mg, 58%). C6H10O2, MW: g/mol. 1H-NMR (CDCl3, 300 MHz): δ = (m, 1 H), (m, 2 H), 3.67 (s, 3 H), (m, 4 H). The analytical data are in accordance with the literature.[13] Following a literature procedure,[13] a solution of crotonaldeyhde (9.98 equiv., mmol, 1.84 g) in CH2Cl2 (10 ml) was added to a solution of the ester (1.00 equiv., 2.63 mmol, mg) in CH2Cl2 (3 ml). Second generation Hoveyda-Grubbs catalyst (0.03 equiv, 0.08 mmol, 49.5 mg) was added and the mixture was stirred for 2 h at 40 C. Subsequently the solvent was removed under reduced pressure and the crude product was purified by silica gel chromatography (hexane/ethyl acetate = 4:1) to yield the unsaturated aldehyde as a colorless oil (2.25 mmol, mg, 86%). C7H10O3, MW: g/mol. 1H-NMR (CDCl3, 300 MHz): δ = 9.51 (d, J = 8.1, 1 H), 6.86 (dt, J = 15.7, 6.3, 1 H), (m, 1 H), 3.70 (s, 3 H), (m, 2 H), (m, 2 H). The other analytical data are in accordance with the literature.[13] S10

11 According to a literature procedure,[14] to a solution of the unsaturated aldehyde (1.00 equiv., 2.25 mmol, mg) in MeOH (10 ml) at 0 C was added sodium borohydride (1.20 equiv., 2.70 mmol, mg). After being stirred for 1 h at 0 C, the reaction was quenched by the addition of saturated aqueous NH4Cl (5 ml) and water (18 ml). Subsequently the mixture was extracted with CH2Cl2 (3 times 10 ml), the combined organic layers were dried over Na2SO4 and the solvent removed under reduced pressure. Purification of the crude product by silica gel chromatography (petrol ether/ethyl acetate = 3:1) yielded the alcohol 4f as a colorless oil (1.49 mmol, mg, 66%). C7H12O3, MW: g/mol. 1H-NMR (CDCl3, 300 MHz): δ = (m, 2 H), (m, 2 H), 3.68 (s, 3 H), (m, 4 H), 1.34 (t, J = 5.8, 1 H). The other analytical data are in accordance with the literature.[14] Synthesis of N-Sulfonyl Protected Allylic Carbamates (1, 5, 8) (E)-Hex-2-en-1-yl tosylcarbamate (1a) According to GP1, (E)-hex-2-en-1-ol (4a, 1 equiv., 1.01 mmol, mg, 120 µl) was treated with ptosylisocyanate (1 equiv., 1.01 mmol, mg, 153 µl) in CH2Cl2 (1 ml) to yield 1a after purification by column chromatography (petrol ether/ethyl acetate = 5/1) as a colorless oil (1.00 mmol, mg, 99%). C14H19NO4S, MW: g/mol. 1H-NMR (CDCl3, 300 MHz): δ = 7.92 (d, J = 8.5, 2 H), 7.40 (b d, J = 8.5, 2 H), (m, 1 H), (m, 1 H), 4.50 (dd, J = 6.6, 0.8, 2 H), 2.44 (s, 3 H), 1.99 (bq, J = 7.4, 2 H) 1.37 (pseudo hex, J = 7.4, 2 H), 0.87 (t, J = 7.4, 3 H). 13C-NMR (CDCl3, 75 MHz): δ = 150.2, 145.1, 138.0, 135.5, 129.6, 128.5, 122.6, 67.7, 34.2, 21.9, 21.7, IR (CDCl3): ν = 3237, 2958, 2929, 1748, 1797, 1446, 1347, 1308, 1290, 1221, 1156, 1089, 1019, 971, 929, 852, 814, 771, 704, 662, 583, 546. MS (ESI) m/z: (5%, [M+K]+), (100%, [M+Na]+), (3%), (6%). HRMS (ESI) m/z: calculated for C14H19NO4S + Na+: ; found: S11

12 (E)-But-2-en-1-yl tosylcarbamate (1c) According to GP1, (E)-but-2-en-1-ol (4c, 1 equiv., 7.52 mmol, 2.71 g of a 20% stem solution in CH2Cl2) was treated with p-tosylisocyanate (1 equiv., 7.05 mmol, 1.48 g, 1.01 ml) in CH2Cl2 (7.5 ml) to yield 1c after purification by column chromatography (petrol ether/ethyl acetate = 4/1) as a colourless oil (5.31 mmol, 1.43 g, 71%). C12H15NO4S, MW: g/mol. 1H-NMR (CDCl3, 300 MHz): δ = 7.95 (d, J = 8.5, 2 H), 7.44 (b, 1 H), 7.36 (d, J = 8.5, 2 H), (m, 1 H), (m, 1 H), 4.51 (dt, J = 6.7, 1.0, 2 H), 2.47 (s, 3 H), 1.69 (d, J = 6.7, 3 H). The other analytical data are in accordance with the literature.[3] (E)-hex-2-en-1-yl (N,N-dimethylsulfamoyl)carbamate (5a) O O S N O O H N 5a According to GP2, a suspension of CDI (1.20 equiv., 1.20 mmol, mg) in CH2Cl2 (1.5 ml) was treated with (E)-hex-2-en-1-ol (4e, 1.00 equiv., 1.00 mmol, mg, 120 µl) to yield the activated alcohol (0.99 mmol, mg, 99%) as a colorless oil, which was directly used for the next step without further purification. C10H14N2O2, MW: g/mol. 1H-NMR (CDCl3, 300 MHz): δ = 8.13 (s, 1 H), 7.42 (t, J = 1.4, 1 H), (m, 1 H), (m, 1 H), (m, 1 H), 4.83 (dd, J = 6.8, 0.8, 2 H), 2.07 (bq, J = 7.1, 2 H), 1.43 (pseudo hex, J = 7.4, 2 H), 0.91 (t, J = 7.4, 3 H). 13 C-NMR (CDCl3, 75 MHz): δ = 148.6, 139.1, 137.1, 130.6, 122.2, 117.1, 69.0, 34.3, 21.9, IR (CDCl3): ν = 3134, 2950, 2931, 2873, 1755, 1671, 1525, 1470, 1449, 1398, 1367, 1316, 1288, 1279, 1168, 1095, 1057, 998, 972, 920, 895, 830, 770, 743, 650, 598, 551. MS (ESI) m/z: (1%), 335.2, (3%), (4%), (24%), (18%), (17%), (6%), (1%), (100%, [M+Na]+), (6%, [M+H]+), (1%), (13%), (1%), (3%). HRMS (ESI) m/z: calculated for C10H14N2O2 + Na: ; found: The activated alcohol (1.00 equiv., 0.99 mmol, mg) was dissolved in DMF (1.5 ml) and treated with DMAP (0.99 equiv., 0.98 mmol, mg), Hünig s base (1.00 equiv., 0.99 mmol, mg, 170 µl) and N,N-dimethylsulfamide (1.00 equiv., 0.99 mmol, mg) to yield 5a after purification S12

13 by column chromatography (petrol ether/ethylacetate = 8/1) as a white solid (0.02 mmol, 49.1 mg, 20%, not optimized). C9H18N2O4S, MW: g/mol. Mp: C. 1H-NMR (CDCl3, 300 MHz): δ = 7.34 (b, 1 H), (m, 1 H), (m, 1 H), 4.59 (dd, J = 6.7, 1.0, 2 H), 2.96 (s, 6 H), 2.04 (bq, J = 7.4, 2 H), 1.41 (pseudo hex, J = 7.4, 2 H), 0.90 (t, J = 7.4, 3 H). 13C-NMR (CDCl3, 75 MHz): δ = 151.2, 138.1, 122.8, 67.5, 38.4, 34.2, 21.9, IR (CDCl3): ν = 3248, 2960, 2930, 1749, 1719, 1453, 1434, 1356, 1283, 1222, 1144, 1099, 1059, 971, 924, 843, 772, 713, 588, 522. MS (ESI) m/z: (3%), (100%, [M+Na]+), (1%), (8%). HRMS (ESI) m/z: calculated for C9H18N2O4S + Na: ; found: (E)-oct-2-en-1-yl (N,N-dimethylsulfamoyl)carbamate (5d) According to GP2, a suspension of CDI (1.20 equiv., 1.20 mmol, mg) in CH2Cl2 (1.5 ml) was treated with (E)-oct-2-en-1-ol (4e, 1.00 equiv., 1.00 mmol, mg, 153 µl) to yield the activated alcohol (0.99 mmol, mg, 99%) as a colorless oil, which was directly used for the next step without further purification. C12H18N2O2, MW: g/mol. 1H-NMR (CDCl3, 300 MHz): δ = 8.12 (s, 1 H), 7.41 (t, J = 1.5, 1 H), (m, 1 H), (m, 1 H), (m, 1 H), 4.81 (dd, J = 6.7, 0.8, 2 H), 2.08 (bq, J = 7.1, 2 H), (m, 6 H), 0.87 (t, J = 7.1, 3 H). 13C-NMR (CDCl3, 75 MHz): δ = 148.6, 139.4, 137.1, 130.6, 122.0, 117.1, 69.0, 32.2, 31.3, 28.4, 22.5, IR (CDCl3): ν = 2957, 2927, 2873, 2856, 1758, 1713, 1570, 1613, 1525, 1468, 1450, 1398, 1367, 1316, 1288, 1279, 1168, 1095, 1057, 1000, 973, 921, 895, 830, 770, 740, 699, 650, 598. MS (ESI) m/z: (1%), (12%), (19%), (1%), (5%), (1%), (100%, [M+Na]+), (15%), (2%), (3%). HRMS (ESI) m/z: calculated for C12H18N2O2 + Na: ; found: The activated alcohol (1.00 equiv., 0.99 mmol, mg) was dissolved in DMF (1.5 ml) and treated with DMAP (0.99 equiv., 0.98 mmol, mg), Hünig s base (1.00 equiv., 0.99 mmol, mg, 170 µl) and N,N-dimethylsulfamide (1.00 equiv., 0.99 mmol, mg) to yield 5x after purification by column chromatography (petrol ether/ethylacetate = 9/1) as a colorless oil (0.12 mmol, 34.4 mg, 12%, not optimized). C11H22N2O4S, MW: 278,37 g/mol. 1H-NMR (CDCl3, 300 MHz): δ = 7.10 (s, 1 H), (m, 1 H), (m, 1 H), 4.58 (dd, J = 6.6, 0.7, 2 H), 2.97 (s, 6 H), 2.05 (bq, J = 7.2, 2 H), (m, 6 H), 0.88 (t, J = 6.9, 3 H). 13C-NMR (CDCl3, 75 MHz): δ = 151.1, 138.4, 122.6, 67.6, 38.4, 32.2, S13

14 31.3, 28.4, 22.5, IR (CDCl3): ν = 3261, 2958, 2927, 2856, 2360, 1749, 1719, 1468, 1453, 1357, 1283, 1216, 1146, 1096, 1060, 973, 928, 854, 838, 772, 714, 590. MS (EI) m/z: (5%, [M]+), (1%), (1%), (11%), (27%), (1%), (17%), (92%), 95.1 (11%), 81.1 (31%), 69.1 (100%), 55.0 (66%), 45.1 (87%). HRMS (EI) m/z: calculated for C11H22N2O4S: ; found: (E)-5-Phenylpent-2-en-1-yl (N,N-dimethylsulfamoyl)carbamate (5e) According to GP2, to a suspension of CDI (1.20 equiv., 1.20 mmol, mg) in CH2Cl2 (1.5 ml) was added (E)-5-phenylpent-2-en-1-ol (4e, 1.00 equiv., 1.00 mmol, mg) dissolved in CH2Cl2 (1.5 ml) dropwise at room temperature to yield the activated alcohol (0.98 mmol, mg, 98%) as a slightly yellow oil, which was directly used for the next step without further purification. C15H16N2O2, MW: g/mol. 1H-NMR (CDCl3, 300 MHz): δ = 8.13 (s, 1 H), (m, 1 H), (m, 2 H), (m, 3 H), (m, 1 H), (m, 1 H), (m, 1 H), 4.81 (dd, J = 6.7, 0.8, 2 H), 2.73 (pseudo t, J = 7.6, 2 H), 2.43 (pseudo q, J = 7.6, 2 H). 13C-NMR (CDCl3, 75 MHz): δ = 141.1, 138.0, 137.1, 130.6, , , 126.0, 122.9, 117.1, 68.7, 35.1, IR (CDCl3): ν = 3026, 2924, 2854, 2359, 1756, 1671, 1603, 1525, 1495, 1471, 1452, 1398, 1367, 1317, 1289, 1279, 1166, 1095, 1057, 1002, 972, 918, 896, 831, 770, 746, 700, 650, 598, 551. MS (ESI) m/z: (100%, [M+Na]+), (6%, [M+H]+), (2%), (14%), (6%), (1%), 91.1 (1%). HRMS (ESI) m/z: calculated for C15H16N2O2 + Na: ; found: The activated alcohol (1.00 equiv., 0.98 mmol, mg) was dissolved in DMF (1.5 ml) and treated with DMAP (1.00 equiv., 0.98 mmol, mg), Hünig s base (1.01 equiv., 0.99 mmol, mg, 170 µl) and N,N-dimethylsulfamide (1.01 equiv., 0.99 mmol, mg) to yield 5e after purification by column chromatography (petrol ether/ethylacetate = 5/1) as a white solid (0.22 mmol, 68.0 mg, 22%, not optimized). C14H20N2O4S, MW: g/mol. Mp: C. 1H-NMR (CDCl3, 300 MHz): δ = (m, 2 H), (m, 3 H), 7.09 (bs, 1 H), (m, 1 H), (m, 1 H), 4.58 (dd, J = 6.5, 0.8, 2 H), 2.96 (s, 6 H), (m, 2 H), 2.39 (pseudo q, J = 7.6, 2 H). 13 C-NMR (CDCl3, 75 MHz): δ = 151.1, 141.3, 136.9, 128.4, 126.0, 123.4, 67.3, 38.4, 35.2, IR (CDCl3): ν = 3258, 3063, 3026, 2944, 2857, 1748, 1720, 1672, 1603, 1496, 1469, 1453, 1432, 1357, 1283, 1220, 1147, 1088, 1060, 974, 927, 850, 773, 749, 717, 700, 586, 541, 522. MS (ESI) m/z: (5%), S14

15 (100%, [M+Na]+), (1%), (5%). HRMS (ESI) m/z: calculated for C14H20N2O4S + Na: ; found: (E)-hex-2-en-1-yl (4-nitrophenyl)sulfonylcarbamate According to GP2, a suspension of CDI (1.20 equiv., 2.40 mmol, mg) in CH2Cl2 (3 ml) was treated with (E)-hex-2-en-1-ol (1.00 equiv., 2.00 mmol, mg, 240 µl) to yield the activated alcohol (1.84 mmol, mg, 92%) as a colorless oil, which was directly used for the next step without further purification. C10H14N2O2, MW: g/mol. 1H-NMR (CDCl3, 300 MHz): δ = 8.13 (s, 1 H), 7.42 (t, J = 1.4, 1 H), (m, 1 H), (m, 1 H), (m, 1 H), 4.83 (dd, J = 6.8, 0.8, 2 H), 2.07 (bq, J = 7.1, 2 H), 1.43 (pseudo hex, J = 7.4, 2 H), 0.91 (t, J = 7.4, 3 H). For the other analytical data see synthesis of 5x. The activated alcohol (1.00 equiv., 1.84 mmol, mg) was dissolved in DMF (3 ml) and treated with DMAP (1.00 equiv., 1.84 mmol, mg), Hünig base (1.00 equiv., 1.84 mmol, mg, 313 µl) and 4-nitrobenzenesulfonamide (1.00 equiv., 1.84 mmol, mg) to yield (E)-hex-2-en-1yl (4-nitrophenyl)sulfonylcarbamate after purification by column chromatography (petrol ether/ethylacetate = 7/1 + 1%AcOH) as a white solid (0.67 mmol, mg, 36%). C13H16N2O6S, MW: g/mol. Mp: C. 1H-NMR (CDCl3, 300 MHz): δ = (m, 2 H), (m, 2 H), 7.48 (b, 1 H), (m, 1 H), (m, 1 H), 4.53 (dd, J = 6.8, 0.6, 2 H), 2.01 (bq, J = 7.4, 2 H), 1.38 (pseudo hex, J = 7.4, 2 H), 0.87 (t, J = 7.4, 3 H). 13 C-NMR (CDCl3, 75 MHz): δ = 150.8, 150.0, 143.9, 138.8, 129.9, 124.2, 122.2, 68.3, 34.2, 31.2, 21.9, IR (CDCl3): ν = 3220, 3107, 2960, 2931, 2873, 1754, 1722, 1608, 1532, 1465, 1451, 1435, 1403, 1348, 1312, 1276, 1224, 1162, 1089, 1013, 973, 929, 873, 848, 771, 737, 683, 610, 576. MS (ESI) m/z: (1%), (8%), (100%), (22%), (100%, [M+Na]+), (2%), (7%), (25%), (1%), (5%), (12%). HRMS (ESI) m/z: calculated for C13H16N2O6S + Na: ; found: S15

16 (E)-Hex-2-en-1-yl (phenylsulfonyl)carbamate (8) According to GP1, (E)-hex-2-en-1-ol (4a, 1 equiv., 1.01 mmol, mg, 120 µl) was treated with benzenesulfonylisocyanate (1 equiv., 1.01 mmol, mg, 135 µl) in CH2Cl2 (1 ml) to yield 8 after purification by column chromatography (petrol ether/ethyl acetate = 5/1) as a white solid (0.94 mmol, mg, 93%). C13H17NO4S, MW: g/mol. Mp: C. 1H-NMR (CDCl3, 300 MHz): δ = (m, 2 H), (m, 1 H), (m, 2 H), 7.41 (b, 1 H), (m, 1 H), (m, 1 H), 4.51 (dd, J = 6.6, 0.8, 2 H), 2.00 (bq, J = 7.4, 2 H), 1.37 (pseudo hex, J = 7.4, 2 H), 0.88 (t, J = 7.4, 3 H). 13 C-NMR (CDCl3, 75 MHz): δ = 150.1, 138.4, 138.2, 134.0, 129.0, 128.4, 122.5, 67.8, 34.2, 21.9, IR (CDCl3): ν = 3251, 3229, 2960, 2931, 2873, 1754, 1721, 1672, 1585, 1451, 1435, 1379, 1352, 1313, 1290, 1217, 1158, 1090, 1053, 1025, 972, 929, 853, 773, 756, 721, 687, 592, 569, 540. MS (ESI) m/z: (13%), (100%, [M+Na]+), (24%), (10%), (4%). HRMS (ESI) m/z: calculated for C13H17NO4S + Na+: ; found: Synthesis of N-Sulfonyl Protected Allylic Amines (2, 6, 9) (R)-N-(Hex-1-en-3-yl)-4-methylbenzenesulfonamide (2a) According to GP5, (E)-hex-2-en-1-ol (4a, 1.00 equiv., 67.9 µmol, 6.8 mg, 8 µl) was treated with ptosylisocyanate (1.01 equiv., 68.9 µmol, 13.6 mg, 10.5 µl), proton sponge (0.20 equiv., 13.5 µmol, 2.9 mg) and [PPFOP-Cl]2 (0.01 equiv, 0.7 µmol, 1.1 mg) in CHCl3 (100 µl) to yield 2a after purification by column chromatography (petrol ether/ethyl acetate = 8/1 + 3 vol% NEt3) as a white solid (54.3 µmol, 13.7 mg, 80%, ee = 90%). The enantiomeric excess was determined by HPLC: chiracel ODH, n-hexane/i-proh (94/6), 1.0 ml min 1, 250 nm, 8.99 min (major enantiomer), min (minor enantiomer). C12H17NO2S, MW: g/mol. Mp: C. [α]d20: 14.1 (c = 0.64, CHCl3, sample with ee = 90%). 1H-NMR (CDCl3, 300 MHz): δ = 7.73 (d, J = 8.4, 2 H), 7.27 (d, J = 8.4, 2 H), (m, 1 H), (m, 2 H), 4.41 (bd, J = 8.0, 1 H), (m, 1 H), 2.42 (s, 3 H), (m, S16

17 2 H), (m, 2 H), 0.83 (t, J = 7.2, 3 H). The other analytical data are in accordance with the literature.[3] Enantiopure crystals suitable for X-ray crystal structure analysis were obtained by slowly evaporating a solution of 2a in n-hexane/i-proh (98/2). CCDC contains the supplementary crystallographic data for this compound. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via The absolute configuration of N-(hex-1-en-3-yl)-4-methylbenzenesulfonamide has already been previously determined.[15] (S)-N-(Hex-1-en-3-yl)-4-methylbenzenesulfonamide (2a) According to GP5, (Z)-hex-2-en-1-ol ((Z)-4a, 1.00 equiv., µmol, 13.6 mg, 16 µl) was treated with p-tosylisocyanate (1.01 equiv., µmol, 27.2 mg, 21 µl), proton sponge (0.20 equiv., 27.0 µmol, 5.8 mg) and [PPFOP-Cl]2 (0.01 equiv, 1.4 µmol, 2.2 mg) in CHCl3 (100 µl) to yield 2a after purification by column chromatography (petrol ether/ethyl acetate = 8/1 + 3 vol% NEt3) as a white solid (39.1 µmol, 9.9 mg, 29%, ee = 75%). The enantiomeric excess was determined by HPLC: chiracel ODH, n-hexane/i-proh (94/6), 1.0 ml min 1, 250 nm, min (minor enantiomer), min (major enantiomer). C12H17NO2S, MW: g/mol. Mp: C. [α]d20: (c = 0.26, CHCl3, sample with ee = 75%). 1H-NMR (CDCl3, 300 MHz): δ = 7.73 (d, J = 8.4, 2 H), 7.27 (d, J = 8.4, 2 H), (m, 1 H), (m,2 H), 4.41 (bd, J = 8.0, 1 H), (m, 1 H), 2.42 (s, 3 H), (m, 2 H), (m, 2 H), 0.83 (t, J = 7.2, 3 H). The other analytical data are in accordance with the literature.[3] The absolute configuration of N-(hex-1-en-3-yl)-4-methylbenzenesulfonamide has already been previously determined.[15] (R)-4-Methyl-N-(pent-1-en-3-yl)benzenesulfonamide (2b) According to GP5, (E)-pent-2-en-1-ol (4b, 1.00 equiv., 68.5 µmol, 5.9 mg, 7 µl) was treated with ptosylisocyanate (1.01 equiv., 68.9 µmol, 13.6 mg, 10.5 µl), proton sponge (0.20 equiv., 13.7 µmol, S17

18 2.9 mg) and [PPFOP-Cl]2 (0.01 equiv, 0.7 µmol, 1.1 mg) in CHCl3 (100 µl) to yield 2b after purification by column chromatography (petrol ether/ethyl acetate = 8/1 + 3 vol% NEt3) as a white solid (60.2 µmol, 14.4 mg, 88%, ee = 91%). The enantiomeric excess was determined by HPLC: chiracel ODH, n-hexane/i-proh (98/2), 1.0 ml min 1, 250 nm, min (major enantiomer), min (minor enantiomer). C12H17NO2S, MW: g/mol. Mp: C, [α]d20: 6.7 (c = 0.33, CHCl3, sample with ee = 91%). 1H-NMR (CDCl3, 300 MHz): δ = 7.74 (d, J = 8.4, 2 H), 7.28 (d, J = 8.4, 2 H), (m, 1 H), (m, 2 H), 4.44 (bd, J = 8.0, 1 H), (m, 1 H), 2.42 (s, 3 H), 1.50 (pseudo q, J = 7.2, 2 H), 0.82 (t, J = 7.2, 3 H). The other analytical data are in accordance with the literature.[3,16] An absolute configuration of 4-methyl-N-(pent-1-en-3-yl)benzenesulfonamide has already been previously assigned.[17] (R)-N-(But-3-en-2-yl)-4-methylbenzenesulfonamide (2c) According to GP5, (E)-but-2-en-1-ol (4c, 1.00 equiv., 74.3 µmol, 20% stem solution in CH2Cl2) was treated with p-tosylisocyanate (1.01 equiv., 75.0 µmol, 14.8 mg, 11.5 µl), proton sponge (0.20 equiv., 14.9 µmol, 3.2 mg) and [PPFOP-Cl]2 (0.01 equiv, 0.7 µmol, 1.1 mg) in CHCl3 (110 µl) to yield 2c after purification by column chromatography (petrol ether/ethyl acetate = 5/1 + 3 vol% NEt3) as a colorless oil (66.6 µmol, 15.0 mg, 90%, ee = 72%). The enantiomeric excess was determined by HPLC: chiracel ADH, n-hexane/i-proh (95/5), 0.5 ml min 1, 250 nm, min (minor enantiomer), min (major enantiomer). C11H15NO2S, MW: g/mol. [α]d20:.4 (c = 0.36, CHCl3, sample with ee = 72%). 1H-NMR (CDCl3, 250 MHz): δ = 7.75 (d, J = 8.4, 2 H), 7.29 (d, J = 8.4, 2 H), (m, 1 H), (m, 2 H), 4.42 (bd, J = 8.0, 1 H), (m, 1 H), 2.42 (s, 3 H), 1.17 (d, J = 7.0, 3 H). The other analytical data are in accordance with the literature.[2,3,16] An absolute configuration of N-(but-3-en-2-yl)-4-methylbenzenesulfonamide has already been previously assigned.[18] S18

19 (R)-4-Methyl-N-(oct-1-en-3-yl)benzenesulfonamide (2d) According to GP5, (E)-oct-2-en-1-ol (4d, 1.00 equiv., 2.62 mmol, mg, 400 µl) was treated with p-tosylisocyanate (1.00 equiv., 2.62 mmol, mg, 400 µl), proton sponge (0.20 equiv., 0.52 mmol, mg) and [PPFOP-Cl]2 (0.01 equiv, 26.3 µmol, 43.0 mg) in CHCl3 (4.0 ml) to yield 2d after purification by column chromatography (petrol ether/ethyl acetate = 8/1 + 3 vol% NEt3) as a white solid (2.22 mmol, mg, 85%, ee = 93%). The enantiomeric excess was determined by HPLC: chiracel ODH, n-hexane/i-proh (98/2), 1.0 ml min 1, 250 nm, min (major enantiomer), min (minor enantiomer). C15H23NO2S, MW: g/mol. Mp: C. [α]d23: 18.6 (c = 2.14, CHCl3, sample with ee = 93%). 1H-NMR (CDCl3, 250 MHz): δ = 7.73 (d, J = 8.4, 2 H), 7.28 (d, J = 8.4, 2 H), (m, 1 H), (m, 2 H), 4.36 (bd, J = 8.0, 1 H), (m, 1 H), 2.42 (s, 3 H), (m, 2 H), (m, 6 H), 0.83 (t, J = 7.2, 3 H). The other analytical data are in accordance with the literature.[19] The absolute configuration of 4-methyl-N-(oct-1-en-3-yl)benzenesulfonamide has already been previously determined.[20] (R)-4-Methyl-N-(5-phenylpent-1-en-3-yl)benzenesulfonamide (2e) According to GP5, (E)-5-phenylpent-2-en-1-ol (4e, 1.00 equiv., 80.1 µmol, 13.0 mg) was treated with p-tosylisocyanate (1.02 equiv., 81.8 µmol, 16.1 mg, 12.5 µl), proton sponge (0.20 equiv., 16.0 µmol, 3.4 mg) and [PPFOP-Cl]2 (0.01 equiv, 0.8 µmol, 1.3 mg) in CHCl3 (120 µl) to yield 2e after purification by column chromatography (petrol ether/ethyl acetate = 5/1 + 3 vol% NEt3) as a white solid (68.8 µmol, 21.7 mg, 86%, ee = 92%). The enantiomeric excess was determined by HPLC: chiracel ODH, n-hexane/i-proh (94/6), 1.0 ml min 1, 250 nm, min (major enantiomer), min (minor enantiomer). C18H21NO2S, MW: g/mol. Mp: C. [α]d20: 31.5 (c = 0.53, CHCl3, sample with ee = 92%). 1H-NMR (CDCl3, 250 MHz): δ = 7.71 (d, J = 8.4, 2 H), (m, 5 H), (m, 2 H), (m, 1 H), (m, 2 H), 4.46 (bd, J = 8.0, 1 H), (m, 1 H), (m, S19

20 2 H), 2.42 (s, 3 H), 1.78 (bq, J = 7.7, 2 H). The other analytical data are in accordance with the literature.[21] Methyl (R)-4-((4-methylphenyl)sulfonamido)hex-5-enoate (2f) According to GP5, methyl (E)-6-hydroxyhex-4-enoate (4f, 1.00 equiv., 70.0 µmol, 10.1 mg) was treated with p-tosylisocyanate (1.03 equiv., 72.0 µmol, 14.2 mg, 11.0 µl), proton sponge (0.20 equiv., 14.0 µmol, 3.0 mg) and [PPFOP-Cl]2 (0.01 equiv, 0.7 µmol, 1.1 mg) in CHCl3 (100 µl) to yield 2f after purification by column chromatography (petrol ether/ethyl acetate = 4/1 + 3 vol% NEt3) as a colorless oil (57.2 µmol, 17.0 mg, 82%, ee = 90%). The enantiomeric excess was determined by HPLC: chiracel ODH, n-hexane/i-proh (93/7), 1.0 ml min 1, 250 nm, min (major enantiomer), min (minor enantiomer). C14H19NO4S, MW: g/mol. [α]d23: 15.7 (c = 0.36, CHCl3, sample with ee = 90%). 1H-NMR (CDCl3, 300 MHz): δ = 7.72 (d, J = 8.3, 2 H), 7.27 (d, J = 8.3, 2 H), (m, 1 H), (m, 2 H), 4.75 (bd, J = H), (m, 1 H), 3.65 (s, 3 H), 2.41 (s, 3 H), (m, 2 H), (m, 2 H). 13C-NMR (CDCl3, 75 MHz): δ = 173.8, 143.3, 137.9, 137.0, 129.6, 127.2, 116.4, 55.6, 51.8, 30.1, 29.9, IR (CDCl3): ν = 3262, 2953, 2923, 2852, 1737, 1716, 1598, 1495, 1437, 1332, 1288, 1257, 1157, 1094, 1068, 1020, 990, 929, 893, 815, 707, 667, 575, 550. MS (ESI) m/z: (100%, [M+Na]+). HRMS (ESI) m/z: calculated for C14H19NO4S + Na: ; found: (S)-N-(1-((tert-Butyldimethylsilyl)oxy)but-3-en-2-yl)-4-methylbenzenesulfonamide (2g) According to GP5, (E)-4-((tert-butyldimethylsilyl)oxy)but-2-en-1-ol (4g, 1.00 equiv., 50.1 µmol, 10.1 mg) was treated with p-tosylisocyanate (1.04 equiv., 52.3 µmol, 10.3 mg, 8 µl), proton sponge (0.20 equiv., 10.0 µmol, 2.1 mg) and [PPFOP-Cl]2 (0.01 equiv, 0.5 µmol, 0.8 mg) in CHCl3 (75 µl) to yield 2g after purification by column chromatography (petrol ether/ethyl acetate = 10/1 + 3 vol% NEt3) as a colourless oil (41.6 µmol, 14.8 mg, 83%, ee = 98%). The enantiomeric excess was determined by HPLC: chiracel ODH, n-hexane/i-proh (99/1), 0.8 ml min 1, 250 nm, min (major enantiomer), min (minor enantiomer). S20

21 C17H29NO3SSi, MW: g/mol. [α]d20:.8 (c = 0.38, CHCl3, sample with ee = 98%). 1H-NMR (CDCl3, 300 MHz): δ = 7.73 (d, J = 8.3, 2 H), 7.28 (d, J = 8.3, 2 H), (m, 1 H), (m, 2 H), 4.91 (bd, J = 6.1, 1 H), (m, 1 H), (m, 2 H), 2.42 (s, 3 H), 0.83 (s, 9 H), 0.01 (s, 3 H), 0.03 (s, 3 H). The other analytical data are in accordance with the literature.[3] (S)-N-(1-(Benzyloxy)but-3-en-2-yl)-4-methylbenzenesulfonamide (2h) According to GP5, (E)-4-(benzyloxy)but-2-en-1-ol (4h, 1.00 equiv., 50.5 µmol, 9.0 mg) was treated with p-tosylisocyanate (1.04 equiv., 52.3 µmol, 10.3 mg, 8 µl), proton sponge (0.20 equiv., 10.0 µmol, 2.1 mg) and [PPFOP-Cl]2 (0.01 equiv, 0.5 µmol, 0.8 mg) in CHCl3 (75 µl) to yield 2h after purification by column chromatography (petrol ether/ethyl acetate = 7/1 + 3 vol% NEt3) as a colorless oil (45.3 µmol, 15.0 mg, 90%, ee = 98%). The enantiomeric excess was determined by HPLC: chiracel ODH, n-hexane/i-proh (94/6), 1.0 ml min 1, 250 nm, min (major enantiomer), min (minor enantiomer). C18H21NO3S, MW: g/mol. [α]d20: 10.0 (c = 0.29, CHCl3, sample with ee = 98%). 1H-NMR (CDCl3, 300 MHz): δ = 7.70 (d, J = 8.4, 2 H), (m, 3 H), (m, 4 H), (m, 1 H), (m, 2 H), 4.92 (bd, J = 6.6, 1 H), 4.41 (s, 2 H), (m, 1 H), (m, 2 H), 2.41 (s, 3 H). The other analytical data are in accordance with the literature.[22] The absolute configuration of N-(1-(benzyloxy)but-3-en-2-yl)-4-methylbenzenesulfonamide has already been previously determined.[22,23] (R)-4-Methyl-N-(4-methylpent-1-en-3-yl)benzenesulfonamide (2i) According to GP5, (E)-4-methylpent-2-en-1-ol (4i, 1.00 equiv., 75.5 µmol, 8.4 mg of a 90% stem solution in CH2Cl2) was treated with p-tosylisocyanate (1.04 equiv., 78.5 µmol, 15.5 mg, 12.0 µl), proton sponge (0.20 equiv., 15.4 µmol, 3.3 mg) and [PPFOP-Cl]2 (0.01 equiv, 0.7 µmol, 1.1 mg) in CHCl3 (100 µl) to yield 2i after purification by column chromatography (petrol ether/ethyl acetate = 10/1 + 3 vol% NEt3) as a white solid (39.5 µmol, 10.0 mg, 52%, ee = 92%). The enantiomeric excess was determined by HPLC: chiracel ODH, n-hexane/i-proh (98/2), 1.0 ml min 1, 250 nm, min (major enantiomer), min (minor enantiomer). S21

22 C13H19NO2S, MW: g/mol. Mp: C. [α]d23: 31.4 (c = 0.29, CHCl3, sample with ee = 92%). 1H-NMR (CDCl3, 250 MHz): δ = 7.72 (d, J = 8.0, 2 H), 7.26 (d, J = 8.0, 2 H), (m, 1 H), (m, 2 H), 4.46 (bs, J = 8.7, 1 H), (m,1 H), 2.41 (s, 3 H), (m, 1 H), 0.77 (d, J = 6.7, 6 H). The other analytical data are in accordance with the literature.[24] An absolute configuration of 4-methyl-N-(4-methylpent-1-en-3-yl)benzenesulfonamide has already been previously assigned.[24] (R)-4-Methyl-N-(5-methylhex-1-en-3-yl)benzenesulfonamide (2j) According to GP5, (E)-5-methylhex-2-en-1-ol (4j, 1.00 equiv., 73.6 µmol, 8.85 mg of a 95% stem solution in CH2Cl2) was treated with p-tosylisocyanate (1.02 equiv., 75.2 µmol, 14.8 mg, 11.5 µl), proton sponge (0.20 equiv., 14.9 µmol, 3.2 mg) and [PPFOP-Cl]2 (0.01 equiv, 0.7 µmol, 1.1 mg) in CHCl3 (100 µl) to yield 2j after purification by column chromatography (petrol ether/ethyl acetate = 10/1 + 3 vol% NEt3) as a white solid (58.0 µmol, 15.5 mg, 79%, ee = 89%). The enantiomeric excess was determined by HPLC: chiracel ODH, n-hexane/i-proh (98/2), 1.0 ml min 1, 250 nm, min (major enantiomer), min (minor enantiomer). C14H21NO2S, MW: g/mol. Mp: C. [α]d23: 14.7 (c = 0.49, CHCl3, sample with ee = 89%). 1H-NMR (CDCl3, 250 MHz): δ = 7.74 (d, J = 8.4, 2 H), 7.27 (d, J = 8.4, 2 H), (m, 1 H), (m, 2 H), 4.52 (bd, J = 8.1, 1 H), (m, 1 H), 2.42 (s, 3 H), 1.60 (hep, J = 6.7, 1 H), (m, 2 H), 0.83 (d, J = 6.6, 3 H), 0.80 (d, J = 6.6, 3 H). The other analytical data are in accordance with the literature.[3] An absolute configuration of 4-methyl-N-(4-methylpent-1-en-3-yl)benzenesulfonamide has already been previously assigned.[25] (R)-N-(hex-1-en-3-yl)-N,N-dimethylsulfamide (6a) According to GP4, (E)-hex-2-en-1-yl (N,N-dimethylsulfamoyl)carbamate (5a, 1.00 equiv, µmol, 40.0 mg) was treated with proton sponge (0.20 equiv., 31.7 µmol, 6.8 mg) and the activated catalyst (prepared as described in GP3 from [PPFOP-Cl]2 and Ag(F3CCO2)), which was added as a stock solution in CH2Cl2 (0.01 equiv., 1.6 µmol, 200 µl, c = 8.0 µmol/ml), for 24 h at 60 C to yield 6a S22

23 after purification by column chromatography (petrol ether/ethyl acetate = 7/1 + 3 vol% NEt3) as a colorless oil (135.7 µmol, 28.0 mg, 85%, ee = 94%). The enantiomeric excess was determined after deprotection and following tosyl protection (see 7a). C8H18N2O2S, MW: g/mol. [α]d23: 19.1 (c = 0.83, CHCl3, sample with ee = 94%). 1H-NMR (CDCl3, 300 MHz): δ = (m, 1 H), (m, 2 H), 4.07 (bd, J = 8.0, 1 H), (m, 1 H), 2.77 (s, 6 H), (m, 2 H), (m, 2 H), 0.92 (t, J = 7.2, 3 H). 13C-NMR (CDCl3, 75 MHz): δ = 138.8, 115.7, 56.6, 38.0, 37.9, 18.7, IR (CDCl3): ν = 3299, 3285, 3082, 3013, 2960, 2934, 2874, 2848, 1734, 1644, 1458, 1431, 1380, 1338, 1321, 1257, 1191, 1147, 1089, 1053, 1031, 994, 956, 920, 839, 744, 708, 585. MS (ESI) m/z: (100%, [M+Na]+). HRMS (ESI) m/z: calculated for C8H18N2O2S + Na: ; found: (R)-N-(oct-1-en-3-yl)-N,N-dimethylsulfamide (6d) According to GP4, (E)-oct-2-en-1-yl (N,N-dimethylsulfamoyl)carbamate (5d, 1.00 equiv, µmol, 40.0 mg) was treated with proton sponge (0.20 equiv., 28.9 µmol, 6.2 mg) and the activated catalyst (prepared as described in GP3 from [PPFOP-Cl]2 and Ag(F3CCO2)), which was added as a stock solution in CH2Cl2 (0.01 equiv., 1.4 µmol, 175 µl, c = 8.0 µmol/ml), for 24 h at 60 C to yield 6d after purification by column chromatography (petrol ether/ethyl acetate = 10/1 + 3 vol% NEt3) as a colorless oil (136.1 µmol, 31.9 mg, 95%, ee = 94%). The enantiomeric excess was determined after deprotection and following tosyl protection (see 7d). C10H22N2O2S, MW: g/mol. [α]d23: 20.9 (c = 1.01, CHCl3, sample with ee = 94%). 1H-NMR (CDCl3, 300 MHz): δ = (m, 1 H), (m, 2 H), 4.10 (bd, J = 8.0, 1 H), (m, 1 H), 2.77 (s, 6 H), (m 2 H), (m, 6 H), 0.87 (t, J = 7.0, 3 H). 13C-NMR (CDCl3, 75 MHz): δ = 138.8, 115.8, 56.8, 38.0, 35.8, 31.5, 25.1, 22.5, IR (CDCl3): ν = 3284, 2958, 2931, 2857, 1739, 1644, 1458, 1430, 1339, 1324, 1256, 1186, 1147, 1052, 1027, 993, 956, 920, 893, 825, 708, 586. MS (ESI) m/z: (100%, [M+Na]+). HRMS (ESI) m/z: calculated for C10H22N2O2S + Na: ; found: S23

24 (R)-N-(5-Phenylpent-1-en-3-yl)-N,N-dimethylsulfamide (6e) According to GP4, (E)-5-phenylpent-2-en-1-yl (N,N-dimethylsulfamoyl)carbamate (5e, 1.00 equiv, µmol, 40.0 mg) was treated with proton sponge (0.20 equiv., 25.6 µmol, 5.4 mg) and the activated catalyst (prepared as described in GP3 from [PPFOP-Cl]2 and Ag(F3CCO2)), which was added as a stock solution in CH2Cl2 (0.01 equiv., 1.2 µmol, 200 µl, c = 6.0 µmol/ml), for 24 h at 50 C to yield 6e after purification by column chromatography (petrol ether/ethyl acetate = 7/1 + 3 vol% NEt3) as a colorless oil (117.8 µmol, 31.6 mg, 92%, ee = 98%). The enantiomeric excess was determined by HPLC: chiracel ADH, n-hexane/i-proh (96/4), 1.0 ml min 1, 250 nm, min (minor enantiomer), min (major enantiomer). Alternatively, referring to GP5, (E)-5-phenylpent-2-en-1-yl (N,N-dimethylsulfamoyl)carbamate (5, 1.00 equiv, µmol, 40.0 mg) was treated with proton sponge (0.20 equiv., 25.6 µmol, 5.4 mg) and [PPFOP-Cl]2 (0.01 equiv, 1.2 µmol, 0.7 mg) in CHCl3 (200 µl) for 24 h at 80 C to yield 6 after purification by column chromatography (petrol ether/ethyl acetate = 7/1 + 3 vol% NEt3) as a colorless oil (119.0 µmol, 31.9 mg, 93%, ee = 96%). The enantiomeric excess was determined by HPLC: chiracel ADH, n-hexane/i-proh (96/4), 1.0 ml min 1, 250 nm, min (major enantiomer), min (minor enantiomer). C13H20N2O2S, MW: g/mol. [α]d23: 26.9 (c = 0.35, CHCl3, sample with ee = 96%). 1H-NMR (CDCl3, 300 MHz): δ = (m, 2 H), (m, 3 H), (m, 1 H), (m, 2 H), 4.29 (bd, J = 8.1, 1 H), (m, 1 H), 2.77 (s, 6 H), 2.69 (bt, J = 8.0, 2 H), (m, 2 H). 13 C-NMR (CDCl3, 75 MHz): δ = 141.1, 138.3, 128.5, 128.4, 126.1, 116.4, 56.4, 38.0, 37.4, IR (CDCl3): ν = 3278, 3085, 3061, 3026, 2950, 2923, 2880, 2846, 1644, 1603, 1497, 1454, 1428, 1341, 1320, 1253, 1191, 1182, 1147, 1086, 1052, 1030, 993, 956, 924, 877, 751, 714, 701, 594, 575, 533, 523. MS (ESI) m/z: (100%, [M+Na]+), (1%, [M+H]+). HRMS (ESI) m/z: calculated for C13H20N2O2S + Na: ; found: S24

25 (R)-N-(hex-1-en-3-yl)-4-nitrobenzenesulfonamide Referring to GP5, (E)-hex-2-en-1-yl (4-nitrophenyl)sulfonylcarbamate (1.00 equiv, µmol, 40.0 mg) was treated with proton sponge (0.20 equiv., 24.3 µmol, 5.2 mg) and [PPFOP-Cl]2 (0.01 equiv, 1.2 µmol, 0.7 mg) in CHCl3 (180 µl) for 24 h at 80 C to yield (R)-N-(hex-1-en-3-yl)-4nitrobenzenesulfonamide after purification by column chromatography (petrol ether/ethyl acetate = 5/1 + 3 vol% NEt3) as a slightly yellow solid (96.7 µmol, 27.5 mg, 80%, ee = 84%). The enantiomeric excess was determined by HPLC: chiracel ASH, n-hexane/i-proh (95/5), 1.0 ml min 1, 250 nm, min (major enantiomer), min (minor enantiomer). C12H16N2O4S, MW: g/mol. Mp: C. [α]d23: 34.1 (c = 0.64, CHCl3, sample with ee = 84%). 1H-NMR (CDCl3, 300 MHz): δ = (m, 2 H), (m, 2 H), (m, 1 H), (m, 2 H), 4.59 (bd, J = 8.2, 1 H), (m, 1 H), (m, 2 H), (m, 2 H), 0.86 (t, J = 7.2, 3 H). 13C-NMR (CDCl3, 75 MHz): δ = 149.9, 147.1, 137.2, 128.4, 124.2, 116.5, 56.7, 37.8, 18.6, IR (CDCl3): ν = 3230, 3283, 3269, 3106, 2961, 2935, 2874, 1645, 1607, 1529, 1466, 1429, 1402, 1350, 1308, 1166, 1110, 1092, 1029, 1012, 991, 932, 855, 737, 686, 617, 564, 532. MS (EI) m/z: (1%, [M]+), (1%), (100%), (1%), (13%), (1%), (1%), (13%), (1%), 92.0 (2%), 76.0 (3%), 54.0 (1%), 41.0 (1%). HRMS (EI) m/z: calculated for C12H16N2O4S: ; found: N-(hex-1-en-3-yl)benzenesulfonamide (Cross-over experiment) (9) According to GP4, a mixture of (E)-But-2-en-1-yl tosylcarbamate (1c, 0.50 equiv., 65.4 µmol, 17.6 mg) and (E)-hex-2-en-1-yl (phenylsulfonyl)carbamate (8, 0.50 equiv, 65.6 µmol, 18.6 mg) was treated with proton sponge (0.20 equiv., 26.2 µmol, 5.6 mg) and the activated catalyst (prepared as described in GP3 from [PPFOP-Cl]2 and Ag(F3CCO2)), which was added as a stock solution in CH2Cl2 (0.02 equiv., 2.60 µmol, 200 µl, c = 13.0 µmol/ml), for 18 h at 50 C to yield 9 after purification by column chromatography (petrol ether/ethyl acetate = 8/1 + 3 vol% NEt3) as a white solid (59.0 µmol, 14.1 mg, 90%). C12H17NO2S, MW: g/mol. Mp: C. 1H-NMR (CDCl3, 300 MHz): δ = (m, 2 H), (m, 3 H), (m, 1 H), (m, 2 H), 4.59 (bd, J = 8.1, 1 H), (m; S25

26 1 H), (m, 2 H), (m, 2 H), 0.83 (t, J = 7.2, 3 H). The other analytical data are in accordance with the literature.[26] 2c was isolated after purification by column chromatography (petrol ether/ethyl acetate = 8/1 + 3 vol% NEt3) as a colorless oil (60.4 µmol, 13.6 mg 92%). For the analytical data see 2c. Synthesis of Allylic Amines (7) (R)-hex-1-en-3-amine (7a) Following a literature procedure,[30] a solution of (R)-N-(hex-1-en-3-yl)-N,N-dimethylsulfamide (6a, 1.00 equiv., 97.3 µmol, 20.1 mg) in 1,3-diaminopropane (100 µl) was heated to 140 C for 2 h. Subsequently the mixture was cooled to room temperature and water (5 ml) was added. The mixture was extracted with CH2Cl2 (3 times 5 ml), the combined organic layers were dried over Na2SO4 and the solvent removed under reduced pressure to yield 7a as a colorless oil (7.2 mg, 72,6 µmol, 75%, ee = 94%). The enantiomeric excess was determined by HPLC after tosyl protection:[31] chiracel ODH, n-hexane/i-proh (94/6), 1.0 ml min 1, 250 nm, 9.35 min (major enantiomer),11.15 min (minor enantiomer). C6H13N, MW: g/mol. 1H-NMR (CDCl3, 300 MHz): δ = (m, 1 H), (m; 2 H), (m, 1 H), (m, 4 H), 1.25 (bs, 2 H), 0.91 (t, J = 7.1, 3 H). The other analytical data are in accordance with the literature.27 (R)-Oct-1-en-3-amine (7d) Following a literature procedure,[28] to a solution of sodium naphthalenide [prepared by stirring a mixture of sodium (5.94 equiv., 2.08 mmol, 48 mg) and naphthalene (6.34 equiv., 2.22 mmol, mg) in THF (4.5 ml) at room temperature for 2 h] was added a solution of (R)-4-methyl-N-(oct1-en-3-yl)benzenesulfonamide (2d, 1.00 equiv., µmol, 98.5 mg, ee = 93%) in THF (2 ml). After stirring at room temperature for 1 h, the reaction was quenched by the addition of ice-water (1.75 ml), acidified with aqueous 1M HCl to ph<1 and the resulting solution was washed with Et2O (3 times 6 ml). Subsequently the aqueous layer was made basic (ph>11) with 30% aqueous NaOH, S26