Rh(I)-catalyzed borylation of primary alkyl chlorides

Tian-Jun Gong Yuan-Ye Jiang Yao Fu

Citation:  Tian-Jun Gong, Yuan-Ye Jiang, Yao Fu. Rh(I)-catalyzed borylation of primary alkyl chlorides[J]. Chinese Chemical Letters, 2014, 25(3): 397-400. doi: 10.1016/j.cclet.2014.01.006 shu

Rh(I)-catalyzed borylation of primary alkyl chlorides

    通讯作者: Yao Fu,
  • 基金项目:

    NSFC (No. 20972148) (No. 20972148)

    CAS (No. KJCX2-EW-J02). We also thank the support of China Postdoctoral Science Foundation (Nos. 2011M500289, 2012T50078). (No. KJCX2-EW-J02)

摘要: Rhodium-catalyzed cross-coupling reactions of unactivated primary alkyl chlorides with diboron reagents have been developed as practical methods for the synthesis of alkylboronic esters. These reactions expand the concept and utility of Rh(I)-catalyzed cross-coupling of aliphatic electrophiles.

English

  • 
    1. [1] M.A. Beenen, C. An, J.A. Ellman, Asymmetric copper-catalyzed synthesis of aamino boronate esters from N-tert-butanesulfinyl aldimines, J. Am. Chem. Soc. 130 (2008) 6910-6911.[1] M.A. Beenen, C. An, J.A. Ellman, Asymmetric copper-catalyzed synthesis of aamino boronate esters from N-tert-butanesulfinyl aldimines, J. Am. Chem. Soc. 130 (2008) 6910-6911.

    2. [2] (a) R. Jana, T.P. Pathak, M.S. Sigman, Advances in transition metal (Pd, Ni, Fe)-catalyzed cross-coupling reactions using alkyl organo-metallics as reaction partners, Chem. Rev. 111 (2011) 1417-1492; (b) C.T. Yang, Z.Q. Zhang, Y.C. Liu, L. Liu, Copper-catalyzed cross coupling reaction of organoboron compounds with primary alkyl halides and pseudohalides, Angew. Chem. Int. Ed. 50 (2011) 3904-3907.[2] (a) R. Jana, T.P. Pathak, M.S. Sigman, Advances in transition metal (Pd, Ni, Fe)-catalyzed cross-coupling reactions using alkyl organo-metallics as reaction partners, Chem. Rev. 111 (2011) 1417-1492; (b) C.T. Yang, Z.Q. Zhang, Y.C. Liu, L. Liu, Copper-catalyzed cross coupling reaction of organoboron compounds with primary alkyl halides and pseudohalides, Angew. Chem. Int. Ed. 50 (2011) 3904-3907.

    3. [3] (a) D.A. Evans, G.C. Fu, A.H. Hoveyda, Rhodium(I)-and iridium(I)-catalyzed hydroboration reactions: scope and synthetic applications, J. Am. Chem. Soc. 114 (1992) 6671-6679; (b) L. Zhang, D. Peng, X. Leng, Z. Huang, Iron-catalyzed, atom-economical, chemoand regioselective alkene hydroboration with pinacolborane, Chem. Int. Ed. 52 (2013) 3676-3680.[3] (a) D.A. Evans, G.C. Fu, A.H. Hoveyda, Rhodium(I)-and iridium(I)-catalyzed hydroboration reactions: scope and synthetic applications, J. Am. Chem. Soc. 114 (1992) 6671-6679; (b) L. Zhang, D. Peng, X. Leng, Z. Huang, Iron-catalyzed, atom-economical, chemoand regioselective alkene hydroboration with pinacolborane, Chem. Int. Ed. 52 (2013) 3676-3680.

    4. [4] (a) M.O. Brien, K.S. Lee, A.H. Hoveyda, Enantioselective synthesis of boronsubstituted quaternary carbons by NHC-Cu-catalyzed boronate conjugate additions to unsaturated carboxylic esters, ketones, or thioesters, J. Am. Chem. Soc. 132 (2010) 10630-10633; (b) Y. Sasaki, Y. Horita, C. Zhong, M. Sawamura, H. Ito, Copper(I)-catalyzed regioselective monoborylation of 1,3-enynes with an internal triple bond: selective synthesis of 1,3-dienylboronates and 3-alkynylboronates, Angew. Chem. Int. Ed. 50 (2011) 2778; (c) J.A. Schiffner, K. Muethner, M. Oestreich, Enantioselective conjugate borylation, Angew. Chem. Int. Ed. 49 (2010) 1194-1196; (d) E. Hartmann, D.J. Vyas, M. Oestreich, Enantioselective formal hydration of a,bunsaturated acceptors: asymmetric conjugate addition of silicon and boron nucleophiles, Chem. Commun. 47 (2011) 7917-7932.[4] (a) M.O. Brien, K.S. Lee, A.H. Hoveyda, Enantioselective synthesis of boronsubstituted quaternary carbons by NHC-Cu-catalyzed boronate conjugate additions to unsaturated carboxylic esters, ketones, or thioesters, J. Am. Chem. Soc. 132 (2010) 10630-10633; (b) Y. Sasaki, Y. Horita, C. Zhong, M. Sawamura, H. Ito, Copper(I)-catalyzed regioselective monoborylation of 1,3-enynes with an internal triple bond: selective synthesis of 1,3-dienylboronates and 3-alkynylboronates, Angew. Chem. Int. Ed. 50 (2011) 2778; (c) J.A. Schiffner, K. Muethner, M. Oestreich, Enantioselective conjugate borylation, Angew. Chem. Int. Ed. 49 (2010) 1194-1196; (d) E. Hartmann, D.J. Vyas, M. Oestreich, Enantioselective formal hydration of a,bunsaturated acceptors: asymmetric conjugate addition of silicon and boron nucleophiles, Chem. Commun. 47 (2011) 7917-7932.

    5. [5] (a) H. Chen, S. Schlecht, T.C. Semple, J.F. Hartwig, Thermal, catalytic, regiospecific functionalization of alkanes, Science 287 (2000) 1995-1997; (b) H. Chen, J.F. Hartwig, Catalytic, regiospecific end-functionalization of alkanes: rhenium-catalyzed borylation under photochemical conditions, Angew. Chem. Int. Ed. 38 (1999) 3391-3393; (c) S. Shimada, A.S. Batsanov, J.A.K. Howard, T.B. Marder, Formation of aryl-and benzylboronate esters by rhodium-catalyzed C-H bond functionalization with pinacolborane, Angew. Chem. Int. Ed. 40 (2001) 2168; (d) J.D. Lawrence, M. Takahashi, C. Bae, J.F. Hartwig, Regiospecific functionalization of methyl C-H bonds of alkyl groups in reagents with heteroatom functionality, J. Am. Chem. Soc. 126 (2004) 15334-15335; (e) J.M. Murphy, J.D. Lawrence, K. Kawamura, C. In-carvito, J.F. Hartwig, Ruthenium-catalyzed regiospecific borylation of methyl C-H Bonds, J. Am. Chem. Soc. 128 (2006) 13684-13685;(f) C.S. Wei, C.A. Jiménez-Hoyos, M.F. Videa, J.F. Hartwig, M.B. Hall, Origins of the selectivity for borylation of primary over secondary C-H bonds catalyzed by Cp*-rhodium complexes, J. Am. Chem. Soc. 132 (2010) 3078-3091; (g) S. Kawamorita, T. Miyazaki, T. Iwai, H. Ohmiya, M. Saw, Rh-catalyzed borylation of N-adjacent C(sp3)-H bonds with a silica-supported triarylphosphine ligand, J. Am. Chem. Soc. 134 (2012) 12924-12927; (h) S. Kawamorita, R. Murakami, T. Iwai, M. Sawamura, Synthesis of primary and secondary alkylboronates through site-selective C(sp3)-H activation with silica-supported monophosphine-Ir catalysts, J. Am. Chem. Soc. 135 (2013) 2947-2950.[5] (a) H. Chen, S. Schlecht, T.C. Semple, J.F. Hartwig, Thermal, catalytic, regiospecific functionalization of alkanes, Science 287 (2000) 1995-1997; (b) H. Chen, J.F. Hartwig, Catalytic, regiospecific end-functionalization of alkanes: rhenium-catalyzed borylation under photochemical conditions, Angew. Chem. Int. Ed. 38 (1999) 3391-3393; (c) S. Shimada, A.S. Batsanov, J.A.K. Howard, T.B. Marder, Formation of aryl-and benzylboronate esters by rhodium-catalyzed C-H bond functionalization with pinacolborane, Angew. Chem. Int. Ed. 40 (2001) 2168; (d) J.D. Lawrence, M. Takahashi, C. Bae, J.F. Hartwig, Regiospecific functionalization of methyl C-H bonds of alkyl groups in reagents with heteroatom functionality, J. Am. Chem. Soc. 126 (2004) 15334-15335; (e) J.M. Murphy, J.D. Lawrence, K. Kawamura, C. In-carvito, J.F. Hartwig, Ruthenium-catalyzed regiospecific borylation of methyl C-H Bonds, J. Am. Chem. Soc. 128 (2006) 13684-13685;(f) C.S. Wei, C.A. Jiménez-Hoyos, M.F. Videa, J.F. Hartwig, M.B. Hall, Origins of the selectivity for borylation of primary over secondary C-H bonds catalyzed by Cp*-rhodium complexes, J. Am. Chem. Soc. 132 (2010) 3078-3091; (g) S. Kawamorita, T. Miyazaki, T. Iwai, H. Ohmiya, M. Saw, Rh-catalyzed borylation of N-adjacent C(sp3)-H bonds with a silica-supported triarylphosphine ligand, J. Am. Chem. Soc. 134 (2012) 12924-12927; (h) S. Kawamorita, R. Murakami, T. Iwai, M. Sawamura, Synthesis of primary and secondary alkylboronates through site-selective C(sp3)-H activation with silica-supported monophosphine-Ir catalysts, J. Am. Chem. Soc. 135 (2013) 2947-2950.

    6. [6] (a) C.T. Yang, Z.Q. Zhang, H. Tajuddin, et al., Alkylboronic esters from coppercatalyzed borylation of primary and secondary alkyl halides and pseudohalides, Angew. Chem. Int. Ed. 51 (2012) 528-532; (b) H. Ito, K. Kubota, Copper(I)-catalyzed boryl substitution of unactivated alkyl halides, Org. Lett. 14 (2012) 890-893; (c) J. Yi, J.H. Liu, J. Liang, et al., Alkylboronic esters from palladium-and nickelcatalyzed borylation of primary and secondary alkyl bromides, Adv. Synth. Catal. 354 (2012) 1685-1691; (d) A.S. Dudnik, G.C. Fu, Nickel-catalyzed coupling reactions of alkyl electrophiles, including unactivated tertiary halides, to generate carbon-boron bonds, J. Am. Chem. Soc. 134 (2012) 10693-10697; (e) A. Joshi-Pangu, X. Ma, M. Diane, et al., Palladium-catalyzed borylation of primary alkyl bromides, J. Org. Chem. 77 (2012) 6629-6633; (f) K. Kubota, E. Yamamoto, H. Ito, Copper(I)-catalyzed borylativeexo-cyclization of alkenyl halides containing unactivated double bond, J. Am. Chem. Soc. 135 (2013) 2635-2640; (g) M. Presset, N. Fleury-Bré geot, D. Oehlrich, F. Rombouts, G.A. Molander, Synthesis and minisci reactions of organotrifluoroborato building blocks, J. Org. Chem. 78 (2013) 4615-4619; (h) H. Li, L. Wang, Y. Zhang, J. Wang, Transition-metal-free synthesis of pinacol alkylboronates from tosylhydrazones, Angew. Chem. Int. Ed. 51 (2012) 2943-2946.[6] (a) C.T. Yang, Z.Q. Zhang, H. Tajuddin, et al., Alkylboronic esters from coppercatalyzed borylation of primary and secondary alkyl halides and pseudohalides, Angew. Chem. Int. Ed. 51 (2012) 528-532; (b) H. Ito, K. Kubota, Copper(I)-catalyzed boryl substitution of unactivated alkyl halides, Org. Lett. 14 (2012) 890-893; (c) J. Yi, J.H. Liu, J. Liang, et al., Alkylboronic esters from palladium-and nickelcatalyzed borylation of primary and secondary alkyl bromides, Adv. Synth. Catal. 354 (2012) 1685-1691; (d) A.S. Dudnik, G.C. Fu, Nickel-catalyzed coupling reactions of alkyl electrophiles, including unactivated tertiary halides, to generate carbon-boron bonds, J. Am. Chem. Soc. 134 (2012) 10693-10697; (e) A. Joshi-Pangu, X. Ma, M. Diane, et al., Palladium-catalyzed borylation of primary alkyl bromides, J. Org. Chem. 77 (2012) 6629-6633; (f) K. Kubota, E. Yamamoto, H. Ito, Copper(I)-catalyzed borylativeexo-cyclization of alkenyl halides containing unactivated double bond, J. Am. Chem. Soc. 135 (2013) 2635-2640; (g) M. Presset, N. Fleury-Bré geot, D. Oehlrich, F. Rombouts, G.A. Molander, Synthesis and minisci reactions of organotrifluoroborato building blocks, J. Org. Chem. 78 (2013) 4615-4619; (h) H. Li, L. Wang, Y. Zhang, J. Wang, Transition-metal-free synthesis of pinacol alkylboronates from tosylhydrazones, Angew. Chem. Int. Ed. 51 (2012) 2943-2946.

    7. [7] S. Ejiri, S. Odo, H. Takahashi, et al., Alkyl-aryl cross-coupling catalyzed by Rh: efficiency of novel tripodal 3-diphenylphosphino-2(diphenylphosphino)-methyl-2-methylpropyl acetate Ligand, Org. Lett. 12 (2010) 1692-1695.[7] S. Ejiri, S. Odo, H. Takahashi, et al., Alkyl-aryl cross-coupling catalyzed by Rh: efficiency of novel tripodal 3-diphenylphosphino-2(diphenylphosphino)-methyl-2-methylpropyl acetate Ligand, Org. Lett. 12 (2010) 1692-1695.

    8. [8] (a) T.J. Gong, B. Xiao, Z.J. Liu, et al., Rhodium-catalyzed selective C-H activation/olefination of phenol carbamates, Org. Lett. 13 (2011) 3235-3237; (b) X.J.Du,Y.H.Tang,X.Zhang,M. Lei,Atheoretical studyonthe alkeneinsertionstep in Rh-Yanphos catalyzed hydroformylation, Chin. Chem. Lett. 24 (2013) 1083-1086; (c) Z.J. Ji, J.Y. Jiang, Y.H. Wang, A novel thermoregulated phosphine ligand used for the Rh-catalyzed hydroformylation of mixed C11-12 olefins in aqueous/organic biphasic system, Chin. Chem. Lett. 21 (2010) 515-518.[8] (a) T.J. Gong, B. Xiao, Z.J. Liu, et al., Rhodium-catalyzed selective C-H activation/olefination of phenol carbamates, Org. Lett. 13 (2011) 3235-3237; (b) X.J.Du,Y.H.Tang,X.Zhang,M. Lei,Atheoretical studyonthe alkeneinsertionstep in Rh-Yanphos catalyzed hydroformylation, Chin. Chem. Lett. 24 (2013) 1083-1086; (c) Z.J. Ji, J.Y. Jiang, Y.H. Wang, A novel thermoregulated phosphine ligand used for the Rh-catalyzed hydroformylation of mixed C11-12 olefins in aqueous/organic biphasic system, Chin. Chem. Lett. 21 (2010) 515-518.

    9. [9] C.T. Yang, Z.Q. Zhang, J. Liang, et al., Copper-catalyzed cross-coupling of nonactivated secondary alkyl halides and tosylates with secondary alkyl grignard reagents, J. Am. Chem. Soc. 134 (2012) 11124-11127.[9] C.T. Yang, Z.Q. Zhang, J. Liang, et al., Copper-catalyzed cross-coupling of nonactivated secondary alkyl halides and tosylates with secondary alkyl grignard reagents, J. Am. Chem. Soc. 134 (2012) 11124-11127.

    10. [10] M. Tobisu, H. Kinuta, Y. Kita, E. Rémond, N. Chatani, Rhodium(I)-catalyzed borylation of nitriles through the cleavage of carbon-cyano bonds, J. Am. Chem. Soc. 134 (2012) 115-118.[10] M. Tobisu, H. Kinuta, Y. Kita, E. Rémond, N. Chatani, Rhodium(I)-catalyzed borylation of nitriles through the cleavage of carbon-cyano bonds, J. Am. Chem. Soc. 134 (2012) 115-118.

    11. [11] B.C. de Pater, E.J. Zijp, H.W. Frü hauf, et al., Oxidative addition reactions of [RhI (Br)(Tpy*)] (Tpy* = 40-(4-ert-butylphenyl)-2,20:60,200-terpyridine) with alkyl bromides, Organometallics 23 (2004) 269-279.[11] B.C. de Pater, E.J. Zijp, H.W. Frü hauf, et al., Oxidative addition reactions of [RhI (Br)(Tpy*)] (Tpy* = 40-(4-ert-butylphenyl)-2,20:60,200-terpyridine) with alkyl bromides, Organometallics 23 (2004) 269-279.

    12. [12] Y.Y. Jiang,H.Z.Yu, Y. Fu,Mechanistic studyof borylation of nitriles catalyzed byRh-B and Ir-B complexes via C-CN bond activation, Organometallics 32 (2013) 926-936.[12] Y.Y. Jiang,H.Z.Yu, Y. Fu,Mechanistic studyof borylation of nitriles catalyzed byRh-B and Ir-B complexes via C-CN bond activation, Organometallics 32 (2013) 926-936.

  • 加载中
计量
  • PDF下载量:  0
  • 文章访问数:  1338
  • HTML全文浏览量:  36
文章相关
  • 发布日期:  2014-01-10
  • 收稿日期:  2013-09-11
  • 网络出版日期:  2013-12-02
通讯作者: 陈斌, bchen63@163.com
  • 1. 

    沈阳化工大学材料科学与工程学院 沈阳 110142

  1. 本站搜索
  2. 百度学术搜索
  3. 万方数据库搜索
  4. CNKI搜索

/

返回文章