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

1.
Department of Chemistry, University of Science and Technology of China, Hefei 230026, China

Corresponding author: Yao Fu,
Received Date: 11 September 2013
Available Online: 2 December 2013
Fund Project: NSFC (No. 20972148) (No. 20972148)

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.
- Alkyl chlorides,
- Rh(I)-catalyzed,
- Cross-coupling,
- Alkylboronic esters
1. [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.
2. [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.
3. [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.
4. [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.
5. [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.
6. [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.
7. [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.
8. [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 C_11-12 olefins in aqueous/organic biphasic system, Chin. Chem. Lett. 21 (2010) 515-518.
9. [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.
10. [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.
11. [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.
12. [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.
1. [1]
  Peng Guo , Shicheng Dong , Xiang-Gui Zhang , Bing-Bin Yang , Jun Zhu , Ke-Yin Ye . Cobalt-catalyzed migratory carbon-carbon cross-coupling of borabicyclo[3.3.1]nonane (9-BBN) borates. Chinese Chemical Letters, 2025, 36(4): 110052-. doi: 10.1016/j.cclet.2024.110052
2. [2]
  Yuhan Liu , Jingyang Zhang , Gongming Yang , Jian Wang . Highly enantioselective carbene-catalyzed δ-lactonization via radical relay cross-coupling. Chinese Chemical Letters, 2025, 36(1): 109790-. doi: 10.1016/j.cclet.2024.109790
3. [3]
  Baokang Geng , Xiang Chu , Li Liu , Lingling Zhang , Shuaishuai Zhang , Xiao Wang , Shuyan Song , Hongjie Zhang . High-efficiency PdNi single-atom alloy catalyst toward cross-coupling reaction. Chinese Chemical Letters, 2024, 35(7): 108924-. doi: 10.1016/j.cclet.2023.108924
4. [4]
  Lang Gao , Cen Zhou , Rui Wang , Feng Lan , Bohang An , Xiaozhou Huang , Xiao Zhang . Unveiling inverse vulcanized polymers as metal-free, visible-light-driven photocatalysts for cross-coupling reactions. Chinese Chemical Letters, 2024, 35(4): 108832-. doi: 10.1016/j.cclet.2023.108832
5. [5]
  Li Li , Zhi-Xin Yan , Chuan-Kun Ran , Yi Liu , Shuo Zhang , Tian-Yu Gao , Long-Fei Dai , Li-Li Liao , Jian-Heng Ye , Da-Gang Yu . Electro-reductive carboxylation of CCl bonds in unactivated alkyl chlorides and polyvinyl chloride with CO₂. Chinese Chemical Letters, 2024, 35(12): 110104-. doi: 10.1016/j.cclet.2024.110104
6. [6]
  Qinghong Zhang , Qiao Zhao , Xiaodi Wu , Li Wang , Kairui Shen , Yuchen Hua , Cheng Gao , Yu Zhang , Mei Peng , Kai Zhao . Visible-light-induced ring-opening cross-coupling of cycloalcohols with vinylazaarenes and enones via β-C-C scission enabled by proton-coupled electron transfer. Chinese Chemical Letters, 2025, 36(2): 110167-. doi: 10.1016/j.cclet.2024.110167
7. [7]
  Xiang Huang , Dongzhen Xu , Yang Liu , Xia Huang , Yangfan Wu , Dongmei Fang , Bing Xia , Wei Jiao , Jian Liao , Min Wang . Asymmetric synthesis of difluorinated α-quaternary amino acids (DFAAs) via Cu-catalyzed difluorobenzylation of aldimine esters. Chinese Chemical Letters, 2024, 35(12): 109665-. doi: 10.1016/j.cclet.2024.109665
8. [8]
  Guang Xu , Cuiju Zhu , Xiang Li , Kexin Zhu , Hao Xu . Copper-catalyzed asymmetric [4+1] annulation of yne–allylic esters with pyrazolones. Chinese Chemical Letters, 2025, 36(4): 110114-. doi: 10.1016/j.cclet.2024.110114
9. [9]
  Chao Chen , Wenwen Yu , Guangen Huang , Xuelian Ren , Xiangli Chen , Yixin Li , Shenggui Liang , Mengmeng Xu , Mingyue Zheng , Yaxi Yang , He Huang , Wei Tang , Bing Zhou . Asymmetric macrocyclization enabled by Rh(Ⅲ)-catalyzed CH activation: Enantioenriched macrocyclic inhibitor of Zika virus infection. Chinese Chemical Letters, 2024, 35(11): 109574-. doi: 10.1016/j.cclet.2024.109574
10. [10]
  Kongchuan Wu , Dandan Lu , Jianbin Lin , Ting-Bin Wen , Wei Hao , Kai Tan , Hui-Jun Zhang . Elucidating ligand effects in rhodium(Ⅲ)-catalyzed arene–alkene coupling reactions. Chinese Chemical Letters, 2024, 35(5): 108906-. doi: 10.1016/j.cclet.2023.108906
11. [11]
  Yuemin Chen , Yunqi Wu , Guoao Wang , Feihu Cui , Haitao Tang , Yingming Pan . Electricity-driven enantioselective cross-dehydrogenative coupling of two C(sp³)-H bonds enabled by organocatalysis. Chinese Chemical Letters, 2024, 35(9): 109445-. doi: 10.1016/j.cclet.2023.109445
12. [12]
  Shulei Hu , Yu Zhang , Xiong Xie , Luhan Li , Kaixian Chen , Hong Liu , Jiang Wang . Rh(Ⅲ)-catalyzed late-stage C-H alkenylation and macrolactamization for the synthesis of cyclic peptides with unique Trp(C7)-alkene crosslinks. Chinese Chemical Letters, 2024, 35(8): 109408-. doi: 10.1016/j.cclet.2023.109408
13. [13]
  Xinghui Yao , Zhouyu Wang , Da-Gang Yu . Sustainable electrosynthesis: Enantioselective electrochemical Rh(III)/chiral carboxylic acid-catalyzed oxidative CH cyclization coupled with hydrogen evolution reaction. Chinese Chemical Letters, 2024, 35(9): 109916-. doi: 10.1016/j.cclet.2024.109916
14. [14]
  Yue Sun , Liming Yang , Yaohang Cheng , Guanghui An , Guangming Li . Pd(I)-catalyzed ring-opening arylation of cyclopropyl-α-aminoamides: Access to α-ketoamide peptidomimetics. Chinese Chemical Letters, 2024, 35(6): 109250-. doi: 10.1016/j.cclet.2023.109250
15. [15]
  Bowen Wang , Longwu Sun , Qianqian Cao , Xinzhi Li , Jianai Chen , Shizhao Wang , Miaolin Ke , Fener Chen . Cu-catalyzed three-component CSP coupling for the synthesis of trisubstituted allenyl phosphorothioates. Chinese Chemical Letters, 2024, 35(12): 109617-. doi: 10.1016/j.cclet.2024.109617
16. [16]
  Qihang Wu , Hui Wen , Wenhai Lin , Tingting Sun , Zhigang Xie . Alkyl chain engineering of boron dipyrromethenes for efficient photodynamic antibacterial treatment. Chinese Chemical Letters, 2024, 35(12): 109692-. doi: 10.1016/j.cclet.2024.109692
17. [17]
  Beitong Zhu , Xiaorui Yang , Lirong Jiang , Tianhong Chen , Shuangfei Wang , Lintao Zeng . A portable and versatile fluorescent platform for high-throughput screening of toxic phosgene, diethyl chlorophosphate and volatile acyl chlorides. Chinese Chemical Letters, 2025, 36(1): 110222-. doi: 10.1016/j.cclet.2024.110222
18. [18]
  Peiyan Zhu , Yanyan Yang , Hui Li , Jinhua Wang , Shiqing Li . Rh(Ⅲ)‐Catalyzed sequential ring‐retentive/‐opening [4 + 2] annulations of 2H‐imidazoles towards full‐color emissive imidazo[5,1‐a]isoquinolinium salts and AIE‐active non‐symmetric 1,1′‐biisoquinolines. Chinese Chemical Letters, 2024, 35(10): 109533-. doi: 10.1016/j.cclet.2024.109533
19. [19]
  Qian Wu , Mengda Xu , Tianjiao Ma , Shuzhen Yan , Jin Li , Xuesong Jiang . Chalcone-derived oxime esters with efficient photoinitiation properties under LED irradiation. Chinese Chemical Letters, 2025, 36(3): 110427-. doi: 10.1016/j.cclet.2024.110427
20. [20]
  Yi Zhu , Jingyan Zhang , Yuchao Zhang , Ying Chen , Guanghui An , Ren Liu . Designing unimolecular photoinitiator by installing NHPI esters along the TX backbone for acrylate photopolymerization and their applications in coatings and 3D printing. Chinese Chemical Letters, 2024, 35(7): 109573-. doi: 10.1016/j.cclet.2024.109573

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(599)
HTML views(17)

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