Please inquire for pricing and availability of listed products to our local sales representatives.

Transcription

1 lease inquire for pricing and availability of listed products to our local sales representatives. 1

2 C- Bond Activation Reaction Recently, there have been a large number of reports on C- bond activation reaction. C- bond activation is a methodology for directly forming carbon-carbon bonds by activating a carbonhydrogen bond, which is the most fundamental linkage in organic chemistry. Traditional cross coupling reactions have been one of the most useful synthetic methods for the formation of carboncarbon bonds. owever, the cross coupling reaction requires extra procedures for preparing organic halides (or triflates) compounds, and organic boron or metal compounds. n the other hand, the C- bond activation can reduce these procedures, thus making this reaction a cost-effective and ecofriendly system. C- Bond Activation Reaction C- Bond Activation + X Metal X =,, Br,, etc. (example) d() + these catalysts in the presence of appropriate ligands and activating reagents. n this brochure, some examples of C- bond activation using palladium catalysts, iridium catalysts, and iron catalysts are shown as below. d() 1) Regio-selective Coupling Reaction of 7,8-Benzoquinoline and Arene Compounds Sanford et al. have reported the direct coupling reaction of 7,8-benzoquinoline and arene compounds using palladium acetate() (A144). ) n this reaction, a nitrogen atom of 7,8-benzoquinoline functions as a directing group to allow it to selectively introduce arenes at the C-10 position. Moreover, arene compounds also react with 7,8-benzoquinoline at the least sterically hindered positions. n this reaction system, 1,4-benzoquinone functions as a reaction promoter, and silver() carbonate oxidizes the generated d(0) species, which forms the d() / d(0) catalytic cycle. cf. Traditional Cross Coupling Reaction X + Y X =, Br,, Tf Y = Sn, B, Zn, Mg (example) Br + () B Cross Coupling Metal d(0) + d(ac) A144 (10 mol%) 1,4-Benzoquinone (0.5 eq.) AgC ( eq.) DMS (4 eq.) 10 C, 1 h C- bonds generally have relatively high energy, therefore, the formation of a carbon-carbon or carbon-heteroatom bond by dissecting C- bonds has been believed to be difficult. n 199, Murai et al. reported the direct addition of C- bonds of aromatic ketones to olefins in the presence of a catalytic amount of carbonyl(dihydrido)tris(triphenylphosphine)ruthenium() (C51). 1) Since then, numerous examples of C- bond activation have been reported. Ru(C)(h ) C51 ( mol%) + Si(Et) Toluene, reflux, h Si(Et) ) Allylic C- xidation using White (Y. 9%) 1,-Bis(phenylsulfinyl)ethane palladium() diacetate (B9) (1) is a palladium catalyst, which was developed by M. C. White et al., and named White catalyst after the developer. For an example of its characteristic reactivity differing from other homogeneous palladium catalysts, the allylic C oxidation reaction has been reported, in which an acetoxy group is introduced regioselectively into the allylic position. ) h S S h d(ac) The reaction above proceeds without using halogenated compounds and organic boron or organic metal compounds. Thus, this system is cost-effective and eco-friendly. R 1 R 1 = C 8 17 B9 (1) 1,4-Benzoquinone ( eq.) Ac, Dioxane, 4 o C Ac R 1 R 1 (7%) ( : = 11 : 1) Ac n general, palladium(), rhodium(), iridium(), ruthenium(), copper(), and iron() are widely used in C- bond activation. There are a number of reports on C- bond activation using Moreover, White et al. have also reported the macrolactonization reaction of ortho-substituted salicylic acid substrates, applying lease inquire for pricing and availability of listed products to our local sales representatives.

3 C- Bond Activation Reaction the reaction into intramolecular allylic C oxidation, in which the corresponding 14-membered ring macrolides are obtained in moderate yields. 4) R 1 (10 mol%) R 1,4-Benzoquinone ( eq.) C, Air, 45 o C 4: R = MM 5: R = Bn 6: R = MM, 57% 7: R = Bn, 57% aryl iodides using iron() acetate (0765). 8) This reaction is highly cost-effective and environmentally friendly in the sense of using an iron catalyst, which is less expensive, and therefore, further development and applications are expected from the point of green chemistry. + Fe(Ac) 0765 (5 mol%) Ligand (10 mol%) K t Bu ( eq.) R 80 C, 0 h R r() Ligand = D0905 Miyaura, shiyama and argwig et al. have reported the direct C- borylation in 00. 5) This reaction is the most famous and practical example of C- bond activation using iridium catalysts. Aryl borates had been synthesized by the reaction of aryl lithium or magnesium reagents with aryl borates so far, however, their method allowed a one-step preparation of aryl borates in a simple manner. Aryl odide roduct (Y. %) (89) [r(cod)] C1807 (1.5 mol%) (60) Ar + B pin Ligand ( mol%) 80 C, 16 h Ar Bpin + Me Me (9) pin = B Arene roduct (Y. %) C Et C Et (40) Ligand = pinb (95%) (79) B0468 pinb (8%) Me pinb Me (7%) Thus, C- bond activation has been widely studied as a new methodology of carbon carbon and carbon-heteroatom bond formations, following a cross coupling reaction and olefin metathesis. Fe() ncluding palladium catalysts, which are frequently used for the Suzuki-Miyaura coupling reaction, transition metal catalysts, such as nickel or platinum, have been widely used for organic synthesis. owever, the percentages of these metals in the earth s crust are extremely small, and their prices are rather expensive. 6) n the other hand, iron is abundant and less expensive, and therefore, more and more chemists have focused their attention to organic synthesis using iron compounds as a catalyst. Cross coupling reactions using iron catalysts have been reported. 7) For an example of C- activation using iron catalysts, Charette et al. have reported the direct coupling reaction of benzene with TC offers a variety of transition metal catalysts, ligands, and activating reagents readily available for C- bond activation as below. lease inquire for pricing and availability of listed products to our local sales representatives.

4 C- Bond Activation Reaction References 1) S. Murai, F. Kakiuchi, S. Sekine, Y. Tanaka, A. Kamatani, M. Sonoda,. Chatani, ature 199, 66, 59. ) K. L. ull, M. S. Sanford, J. Am. Chem. Soc. 007, 19, ) M. S. Chen,. rabagaran,. A. Labenz, M. C. White, J. Am. Chem. Soc. 005, 17, ) K. J. Fraunhoffer,. rabagaran, L. E. Sirois, M. C. White, J. Am. Chem. Soc. 006, 18, 90. 5) T. shiyama, J. Takagi, K. shida,. Miyaura,. R. Anastasi, J. F. artwig, J. Am. Chem. Soc. 00, 14, 90. 6) J. Emsley, in The Elements, rd ed., xford Univ. ress, ew York, ) T. agano, T. ayashi, rg. Lett. 004, 6, 197; K. G. Dongo,. Koh, M. Sau, C. L. L. Chai, Adv. Synth. Catal. 007, 49, 1015; T. atakeyama, M. akamura, J. Am. Chem. Soc. 007, 19, ) F. Vallée, J. J. Mousseau, A. B. Charette, J. Am. Chem. Soc. 010, 1, 1514, A144 B174 alladium Metal s C d alladium() Acetate [75-1-] C C C C C d Bis(dibenzylideneacetone)- palladium(0) [ ] B1676 B018 B055 B9 00mg 1g 1870 ( C) d Bis(acetonitrile)palladium() Dichloride [ ] d Bis(,4-pentanedionato)- palladium() [ ] d Bis(tricyclohexylphosphine)- palladium() Dichloride [ ] S C C d S C C 1,-Bis(phenylsulfinyl)ethane alladium() Diacetate (White ) [ ] CF C d alladium() Trifluoroacetate [ ] B1045 B961 C5 100mg 500mg C461 00mg odium Chloro(1,5-cyclooctadiene)- rhodium() Dimer [ ] BF 4 Bis(1,5-cyclooctadiene)- rhodium() Tetrafluoroborate [518--8] Chlorobis(cyclooctene)- rhodium() Dimer [ ] C C C C C C C C Chlorobis(ethylene)- rhodium() Dimer [ ] mg 1g R0069 T091 (entamethylcyclopentadienyl)- rhodium() Dichloride Dimer [ ] C odium() Acetate Dimer [ ] Tris(triphenylphosphine)rhodium() Chloride [ ] C mg 1g C66 00mg 1g 176 1g ridium r Chloro(1,5-cyclooctadiene)- iridium() Dimer [ ] r r r (1,5-Cyclooctadiene)(methoxy)- iridium() Dimer [ ] r r (entamethylcyclopentadienyl)- iridium() Dichloride Dimer [ ] 4 lease inquire for pricing and availability of listed products to our local sales representatives.

5 C- Bond Activation Reaction B190 C51 50mg 1g D1997 D751 Ruthenium Ru Ru Benzeneruthenium() Chloride Dimer [ ] Ru C Carbonyl(dihydrido)- tris(triphenylphosphine)- ruthenium() [560--1] Ru Tris(triphenylphosphine)- ruthenium() Dichloride [ ] () C Ru Ru C C() Dichloro(p-cymene)ruthenium() Dimer [ ] R0074 T181 C46 5g 500g T19 Ru Ruthenium() Chloride [ ] Ru(C) 4 (C) 4 Ru Ru(C) 4 Triruthenium Dodecacarbonyl [154--1] Copper C Cu. Copper() Acetate Monohydrate [ ] CF S Cu Copper() Trifluoromethanesulfonate [ ] g 100g 500g 0765 ron Tris(,4-pentanedionato)- iron() [ ] Fe C Fe ron() Acetate [ ] B0468 5g 100g 500g B118 B1174 Ligands CCC C,'-Bipyridyl [ ] 1,-Bis(diphenylphosphino)- propane [ ] 1,-Bis(dimethylphosphino)- ethane [ ] B710 D070 5mL 5mL D0771 1g 5g D0905 D1804 Fe C( ) C( ) C( ) C( ) 1,1'-Bis(diisopropylphosphino)- ferrocene [ ] C,'- Dimethylethylenediamine [ ]. 1/ eocuproine emihydrate [ ] Bathophenanthroline [ ] C C C C C,6-Di-tert-butylpyridine [ ] D411 D14 1g 01 1g 5g T0519 5g 500g T104 C( ) C( ). Dicyclohexylphenylphosphine [ ] 4,4'-Di-tert-butyl-,'-bipyridyl [ ] 1,10-henanthroline Monohydrate [ ] Triphenylphosphine [60-5-0] Tri(o-tolyl)phosphine [ ] T1165 5mL 500mL T1614 5g T164 T584 T585 Tricyclohexylphosphine (contains Tricyclohexylphosphine xide) (ca. 18% in Toluene, ca. 0.60mol/L) [6-14-] Tris(,6-dimethoxyphenyl)- phosphine [ ] Tri(-furyl)phosphine [ ] C( ) ( ) C BF 4 C( ) Tri-tert-butylphosphonium Tetrafluoroborate [ ] BF 4 Tricyclohexylphosphonium Tetrafluoroborate [ ] B0089 5g 500g B0887 5g 500g D0686 Additives 1,4-Benzoquinone [ ] 1,4-Benzoquinone [ ] p-xyloquinone [ ] lease inquire for pricing and availability of listed products to our local sales representatives. 5

6 C- Bond Activation Reaction D0798 5g 500g D4 5g S046 T041 5g 100g 500g T144 5g 500g S C Dimethyl Sulfoxide [ ],6-Dimethyl-1,4- benzoquinone [ ] AgSbF 6 Silver exafluoroantimonate(v) [ ] CF Trifluoroacetic Acid [ ] p-toluquinone [ ] T05 100mL Ti 4 Titanium(V) Chloride (14% in Dichloromethane, ca. 1.0mol/L) [ ] 6 lease inquire for pricing and availability of listed products to our local sales representatives.

7 C- Bond Activation Reaction lease inquire for pricing and availability of listed products to our local sales representatives. 7

8 Availability, price or specification of the listed products are subject to change without prior notice. Reproduction forbidden without the prior written consent of Tokyo Chemical ndustry Co., Ltd. R5107E rinted in Japan