Rh（III）催化的N-甲氧基苯甲酰胺系列物选择性C-H氰基化反应

催化学报 , 2015, (8): 1175-1182. doi: 10.1016/S1872-2067(15)60872-5

Rh（III）催化的N-甲氧基苯甲酰胺系列物选择性C-H氰基化反应

张斯维 ^1, , 周杰 ^2, , 施晶晶 ^3, , 王旻 ^4, , 徐华强 ^5, , 易伟 ^6,

1.中国药科大学生命科学与技术学院，江苏南京210009; 中国科学院上海药物研究所，中科院受体结构与功能重点实验室药物靶标与结构功能研究中心，上海201203

2.中国科学院上海药物研究所，中科院受体结构与功能重点实验室药物靶标与结构功能研究中心，上海201203

3.中国科学院上海药物研究所，中科院受体结构与功能重点实验室药物靶标与结构功能研究中心，上海201203

4.中国药科大学生命科学与技术学院,江苏南京,210009

5.中国科学院上海药物研究所，中科院受体结构与功能重点实验室药物靶标与结构功能研究中心，上海201203; Van Andel研究所结构科学与药物发现中心，美国密西根49503

6.中国科学院上海药物研究所，中科院受体结构与功能重点实验室药物靶标与结构功能研究中心，上海201203

基金项目: 上海市自然科学基金(15ZR1447800) 国家博士后科学基金(2012M511158,2013T60477,2014M560363).@@@@This work was supported by Shanghai Municipal Natural Science Foundation, China(15ZR1447800) the Chinese Postdoctoral Science Founda-tion(2012M511158,2013T60477,2014M560363)

关键词： Rh(III)催化剂 , C-H键氰基化 , N-甲氧基苯甲酰胺系列物 , N-氰基-N-苯基对甲苯磺酰胺 , 反应机制

Rh(III)-catalyzed direct C-H cyanation of N-methoxybenzamides using N-cyano-N-phenyl-p-toluenesulfonamide

Keywords： Rhoduim(III) catalyst , C-H cyanation , N-methoxybenzamides , N-cyano-N-phenyl-p-toluenesulfonamide , Reaction mechanism

采用了最近热门的Rh(III)催化C?H键活化方法，以N-甲氧基苯甲酰胺系列物为反应底物， N-氰基-N-苯基对甲苯磺酰胺(NCTS)为氰基化试剂，高效合成了含氰基官能团产物。结果表明，该反应在碳酸银存在下，使用二氧六环作为反应溶剂，于80°C反应8h生成的邻位氰基取代的N-甲氧基苯甲酰胺的产率较高。进一步研究表明，该反应具有好的区域选择性和底物/官能团适应性。一系列机理实验研究表明，该反应可能采用了一个内部的亲电取代机制及使用了C?H键切割步骤作为关键限速步骤。考虑到该反应产物包含有价值的结构单元-N-甲氧基甲酰胺和氰基取代基，因而有望用于现代有机合成中。

A new method has been developed for the mild and efficient Rh(III)-catalyzed direct C?H cyanation of a diverse range of N-methoxybenzamides using N-cyano-N-phenyl-p-toluenesulfonamide as an environmentally friendly and efficient cyanating reagent. This new reaction proceeded with good regioselectivity to provide direct access to a wide variety of valuable ortho-cyanated N-methox-ybenzamides with board substrate/functional group tolerance.

参考文献

[1]	Fatiadi A J.[A].New York:Wiley,1983
[2]	Grundmann C.[A].Stuttgart:Thieme,1985
[3]	Larock R C.Comprehensive Organic Transformations[M].New York:VCH,1989
[4]	Kleemann A;Engel J;Kutscher B.Pharmaceutical Substances:Synthesis, Patents, Applications[M].Stuttgart:Thieme,2001
[5]	Smith M B;March J.March’s Advanced Organic Chemistry:Reac-tions, Mechanisms, and Structure[M].Hoboken:Wiley,2007
[6]	Rappoport Z.The Chemistry of the Cyano Group[M].New York:Inter-science,1970
[7]	Larock R C.Comprehensive Organic Transformations[M].Weinheim:Wiley-VCH,1999
[8]	Kleemann A;Engel J;Kutschner B;Reichert D.Pharmaceutical Substances：Syntheses, Patents, Applications[M].Stuttgart:Thieme,New York,2001
[9]	Miller J S;Manson J L .[J].Acc Chem Res,2001,34:563.
[10]	Anbarasan P;Schareina T;Beller M .[J].Chem Soc Rev,2011,40:5049.
[11]	Rosenmund K W;Struck E .[J].Ber Chem,1919,52B:1749.
[12]	Braun J;Manz G .[J].Liebigs Ann Chem,1931,488:111.
[13]	Lindley J .[J].Tetrahedron,1984,40:1433.
[14]	Enders D.;Shilvock JP. .Some recent applications of alpha-amino nitrile chemistry [Review][J].Chemical Society Reviews,2000(5):359-373.
[15]	Kuo CW;Zhu JL;Wu JD;Chu CM;Yao CF;Shia KS .A convenient new procedure for converting primary amides into nitriles[J].Chemical communications,2007(3):301-303.
[16]	Qin, C.;Jiao, N. .Iron-facilitated direct oxidative C-H transformation of allylarenes or alkenes to alkenyl nitriles[J].Journal of the American Chemical Society,2010(45):15893-15895.
[17]	Anbarasan, P.;Neumann, H.;Beller, M. .A novel and convenient synthesis of benzonitriles: Electrophilic cyanation of aryl and heteroaryl bromides[J].Chemistry: A European journal,2011(15):4217-4222.
[18]	Wang, R.;Falck, J.R. .Rhodium(i)-catalyzed N-CN bond cleavage: Intramolecular β-cyanation of styrenes[J].Chemical communications,2013(58):6516-6518.
[19]	Pawar A B;Chang S .[J].Org Lett,2015,17:660.
[20]	Ellis G P;Romney-Alexander T M .[J].Chem Rev,1987,87:779.
[21]	Anbarasan P;Neumann H;Beller M .[J].Angew Chem Int Ed,2011,50:519.
[22]	Anbarasan, P.;Neumann, H.;Beller, M. .A novel and convenient synthesis of benzonitriles: Electrophilic cyanation of aryl and heteroaryl bromides[J].Chemistry: A European journal,2011(15):4217-4222.
[23]	Kim J;Kim H J;Chang S .[J].Angew Chem Int Ed,2012,51:11948.
[24]	Senecal T D;Shu W;Buchwald S L .[J].Angew Chem Int Ed,2013,52:10035.
[25]	Coppola, A.;Sánchez-Alonso, P.;Sucunza, D.;Burgos, C.;Alajarín, R.;Alvarez-Builla, J.;Mosquera, M.E.G.;Vaquero, J.J. .Remote aryl cyanation via isocyanide-cyanide rearrangement on tosylmethyl isocyanide derivatives[J].Organic letters,2013(13):3388-3391.
[26]	Liu W;Ackermann L .[J].Chem Commun,2014,50:1878.
[27]	Yu D G;Gensch T;de Azambuja F;Vásquez-Céspedes S,Glorius F .[J].J Am Chem Soc,2014,136:17722.
[28]	Li J;Ackermann L .[J].Angew Chem Int Ed,2015,54:3635.
[29]	Nozaki K;Sato N;Takaya H .[J].J Org Chem,1994,59:2679.
[30]	Luo FH.;Cheng CH.;Chu CI. .Nitrile-group transfer from solvents to aryl halides. Novel carbon-carbon bond formation and cleavage mediated by palladium and zinc species[J].Organometallics,1998(6):1025-1030.
[31]	Sundermeier M;Zapf A;Beller M .[J].Angew Chem Int Ed,2003,42:1661.
[32]	Sundermeier M.;Mutyala S.;Zapf A.;Spannenberg A.;Beller M. .A convenient and efficient procedure for the palladium-catalyzed cyanation of aryl halides using trimethylsilylcyanide[J].Journal of Organometallic Chemistry,2003(1/2):50-55.
[33]	Kobayashi Y;Kamisaki H;Yanada R;Takemoto Y .Palladium-catalyzed intramolecular cyanoamidation of alkynyl and alkenyl cyanoformamides[J].Organic letters,2006(13):2711-2713.
[34]	Arai S;Sato T;Koike Y;Hayashi M,Nishida A .[J].Angew Chem Int Ed,2009,48:4528.
[35]	Arai S;Sato T;Nishida A .[J].Adv Synth Catal,2009,351:1897.
[36]	Ding S T;Jiao N .[J].J Am Chem Soc,2011,133:12374.
[37]	Sawant D N;Wagh Y S;Tambade P J;Bhatte K D,Bhanage B M .[J].Adv Synth Catal,2011,353:781.
[38]	Wen Q D;Jin J S;Hu B B;Lu P,Wang Y .[J].RSC Adv,2012,2:6167.
[39]	Yang C T;Han J;Liu J;Gu M,Li Y,Wen J,Yu H Z,Hu S,Wang X L .[J].Org Biomol Chem,2015,13:2541.
[40]	Kou X Z;Zhao M D;Qiao X X;Zhu Y M,Tong X F,Shen Z M .[J].Chem Eur J,2013,19:16880.
[41]	Pan C D;Jin H M;Xu P;Liu X,Cheng Y X,Zhu C J .[J].J Org Chem,2013,78:9494.
[42]	Xu, H.;Liu, P.-T.;Li, Y.-H.;Han, F.-S. .Copper-mediated direct aryl C-H cyanation with azobisisobutyronitrile via a free-radical pathway[J].Organic letters,2013(13):3354-3357.
[43]	Yang Y;Buchwald S L .[J].Angew Chem Int Ed,2014,53:8677.
[44]	Xu L;Mou X Q;Chen Z M;Wang S H .[J].Chem Commun,2014,50:10676.
[45]	Yan Y P;Yuan Y Z;Jiao N .[J].Org Chem Front,2014,1:1176.
[46]	Zhang L P;Lu P;Wang Y G .[J].Chem Commun,2015,51:2840.
[47]	Gong, T.-J.;Xiao, B.;Cheng, W.-M.;Su, W.;Xu, J.;Liu, Z.-J.;Liu, L.;Fu, Y. .Rhodium-catalyzed directed C-H cyanation of arenes with N-cyano-N-phenyl-p-toluenesulfonamide[J].Journal of the American Chemical Society,2013(29):10630-10633.
[48]	Chaitanya, M.;Yadagiri, D.;Anbarasan, P. .Rhodium catalyzed cyanation of chelation assisted C-H bonds[J].Organic letters,2013(19):4960-4963.
[49]	Chaitanya M;Anbarasan P .[J].J Org Chem,2015,80:3695.
[50]	Gu L J;Jin C;Wang R;Ding H Y .[J].ChemCatChem,2014,6:1225.
[51]	Han J;Pan C D;Jia X F;Zhu C J .[J].Org Biomol Chem,2014,12:8603.
[52]	Hong X H;Wang H;Qian G Y;Tan Q T,Xu B .[J].J Org Chem,2014,79:3228.
[53]	Lewis J C;Bergman R G;Ellman J A .[J].Acc Chem Res,2008,41:1013.
[54]	Satoh, T.;Miura, M. .Oxidative coupling of aromatic substrates with alkynes and alkenes under Rhodium Catalysis[J].Chemistry: A European journal,2010(37):11212-11222.
[55]	Wencel-Delord J;Dr?ge T;Liu F;Glorius F .[J].Chem Soc Rev,2011,40:4740.
[56]	Patureau F W;Wencel-Delord J;Glorius F .[J].Aldrichimica Acta,2012,45:31.
[57]	Kuhl N;Hopkinson M N;Wencel-Delord J;Glorius F .[J].Angew Chem Int Ed,2012,51:10236.
[58]	Song G Y;Wang F;Li X W .[J].Chem Soc Rev,2012,41:3651.
[59]	Colby D A;Tsai A S;Bergman R G;Ellman J A .[J].Acc Chem Res,2012,45:814.
[60]	Etayo P;Vidal-Ferran A .[J].Chem Soc Rev,2013,42:728.
[61]	Yan G B;Wu X M;Yang M H .[J].Org Biomol Chem,2013,11:5558.
[62]	Kuhl N;Schr?der N;Glorius F .[J].Adv Synth Catal,2014,356:1443.
[63]	Zhang M;Zhang Y F;Jie X M;Zhao H Q,Li G,Su W P .[J].Org Chem Front,2014,1:843.
[64]	Han Y F;Jin G X .[J].Chem Soc Rev,2014,43:2799.
[65]	He R;Huang Z T;Zheng Q Y;Wang C .[J].Tetrahedron Lett,2014,55:5705.
[66]	Song G Y;Li X W .[J].Acc Chem Res,2015,48:1007.
[67]	Wang DH;Wasa M;Giri R;Yu JQ .Pd(II)-catalyzed cross-coupling of sp(3) C-H bonds with sp(2) and sp(3) boronic acids using air as the oxidant[J].Journal of the American Chemical Society,2008(23):7190-7191.
[68]	Wasa, M;Yu, JQ .Synthesis of beta-, gamma-, and delta-Lactams via Pd(II)-Catalyzed C-H Activation Reactions[J].Journal of the American Chemical Society,2008(43):14058-14059.
[69]	Guimond, N.;Gouliaras, C.;Fagnou, K. .Rhodium(III)-catalyzed isoquinolone synthesis: The N-O bond as a handle for C-N bond formation and catalyst turnover[J].Journal of the American Chemical Society,2010(20):6908-6909.
[70]	Wang G W;Yuan T T .[J].J Org Chem,2010,75:476.
[71]	Karthikeyan J;Cheng C H .[J].Angew Chem Int Ed,2011,50:9880.
[72]	Wrigglesworth, J.W.;Cox, B.;Lloyd-Jones, G.C.;Booker-Milburn, K.I. .New heteroannulation reactions of N-Alkoxybenzamides by Pd(II) Catalyzed C-H activation[J].Organic letters,2011(19):5326-5329.
[73]	Rakshit, S.;Grohmann, C.;Besset, T.;Glorius, F. .Rh(III)-catalyzed Directed C-H Olefination using an oxidizing directing group: Mild, efficient, and versatile[J].Journal of the American Chemical Society,2011(8):2350-2353.
[74]	Guimond, N.;Gorelsky, S.I.;Fagnou, K. .Rhodium(III)-catalyzed heterocycle synthesis using an internal oxidant: Improved reactivity and mechanistic studies[J].Journal of the American Chemical Society,2011(16):6449-6457.
[75]	Wang H G;Glorius F .[J].Angew Chem Int Ed,2012,51:7318.
[76]	Zeng, R.;Fu, C.;Ma, S. .Highly selective mild stepwise allylation of N-methoxybenzamides with allenes[J].Journal of the American Chemical Society,2012(23):9597-9600.
[77]	Zeng R;Wu S Z;Fu C L;Ma S M .[J].J Am Chem Soc,2013,135:18284.
[78]	Yang F Z;Ackermann L .[J].J Org Chem,2014,79:12070.
[79]	Yang W;Sun J Q;Xu X X;Zhang Q,Liu Q .[J].Chem Commun,2014,50:4420.
[80]	Liu Y J;Xu H;Kong W J;Shang M,Dai H X,Yu J Q .[J].Nature,2014,515:389.
[81]	Yu D G;de Azambuja F;Glorius F .[J].Angew Chem Int Ed,2014,53:2754.
[82]	Yang W;Wang S;Zhang Q;Liu Q,Xu X X .[J].Chem Commun,2015,51:661.
[83]	Shi J J;Zhou J;Yan Y N;Jia J L,Liu X L,Song H C,Xu H E,Yi W .[J].Chem Commun,2015,51:668.
[84]	Oxgaard J;Tenn WJ;Nielsen RJ;Periana RA;Goddard WA .Mechanistic analysis of iridium heteroatom C-H activation: Evidence for an internal electrophilic substitution mechanism[J].Organometallics,2007(7):1565-1567.
[85]	Ackermann, L. .Carboxylate-assisted transition-metal-catalyzed C-H bond functionalizations: Mechanism and scope[J].Chemical Reviews,2011(3):1315-1345.
[86]	Ma W B;Ackermann L .[J].Chem Eur J,2013,19:13925.
[87]	Ma W B;Mei R H;Tenti G;Ackermann L .[J].Chem Eur J,2014,20:15248.
[88]	Jia J L;Shi J J;Zhou J;Liu X L,Song Y L,Xu H E,Yi W .[J].Chem Commun,2015,51:2925.
[89]	Ackermann, L.;Lygin, A.V. .Cationic ruthenium(II) catalysts for oxidative C - H/N - H bond functionalizations of anilines with removable directing group: Synthesis of indoles in water[J].Organic letters,2012(3):764-767.
[90]	Ackermann, L.;Wang, L.;Wolfram, R.;Lygin, A.V. .Ruthenium-catalyzed oxidative C - H alkenylations of anilides and benzamides in water[J].Organic letters,2012(3):728-731.
[91]	Qi Z S;Wang M;Li X W .[J].Chem Commun,2014,50:9776.
[92]	Duan P P;Lan X;Chen Y;Qian S S,Li J J,Lu L,Lu Y B,Chen B,Hong M,Zhao J .[J].Chem Commun,2014,50:12135.
[93]	Shen Y Y;Liu G X;Zhou Z;Lu X Y .[J].Org Lett,2013,15:3366.
[94]	Zhou J;Shi J J;Liu X L;Jia J L,Song H C,Xu H E,Yi W .[J].Chem Commun,2015,51:5868.
[95]	戚自松,李兴伟.三价铑催化苯甲酰胺与醌的C-H活化偶联[J].催化学报,2015(1):48-56.
[96]	Simmons E M;Hartwig J F .[J].Angew Chem Int Ed,2012,51:3066.
[97]	Feng C;Loh T P .[J].Angew Chem Int Ed,2014,53:2722.
[98]	Jones W D .[J].Acc Chem Res,2003,36:140.
[99]	Cui S L;Zhang Y;Wu Q F .[J].Chem Sci,2013,4:3421.
[100]	Hu S;Wang D Q;Liu J X;Li X W .[J].Org Biomol Chem,2013,11:2761.
[101]	Zhang Y;Wu Q F;Cui S L .[J].Chem Sci,2014,5:297.
[102]	Liang Y J;Yu K;Li B;Xu S S,Song H B,Wang B Q .[J].Chem Commun,2014,50:6130.
[103]	Li X G;Sun M;Liu K;Jin Q,Liu P N .[J].Chem Commun,2015,51:2380.
[104]	Yu S J;Liu S;Lan Y;Wan B X,Li X W .[J].J Am Chem Soc,2015,137:1623.
[105]	Schro?der N;Lied F;Glorius F .[J].J Am Chem Soc,2015,137:1448.
[106]	Zhao D B;Vásquez-Céspedes S;Glorius F .[J].Angew Chem Int Ed,2015,54:1657.
[107]	甄文萃,杜正银,李兴伟.三价铑催化亚甲胺内盐与丙烯酰胺氧化合成三取代吡唑[J].催化学报,2013(04):679-683.
[108]	张亦猛,张涛,詹豪强,李兴伟.铑（III）催化N-磺酰基2-甲酰苯胺与烯烃环化制备（2H）喹啉[J].催化学报,2014(11):1840-1845.

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