Citation: Meng-Yan Liu, Shi-Bin Hong, Wei Zhang, Wei Deng. Expedient copper-catalyzed borylation reactions using amino acids as ligands[J]. Chinese Chemical Letters, ;2015, 26(3): 373-376. doi: 10.1016/j.cclet.2014.12.004 shu

Expedient copper-catalyzed borylation reactions using amino acids as ligands

Meng-Yan Liu ^a,b ,
Shi-Bin Hong ^a,b ,
Wei Zhang ^a,b ,
Wei Deng ^a,b,,

1.
a Research Center of Nano Science and Technology, Shanghai University, Shanghai 200444, China;
2.
b School of Chemical and Engineering, Shanghai Institute of Technology, Shanghai 201418, China

Corresponding author: Wei Deng,
Received Date: 1 September 2014
Available Online: 24 November 2014
Fund Project: We gratefully acknowledge financial support from the Eastern Scholar, Shanghai Pujiang Program, Key Subject of Shanghai Municipal Education Commission, Natural Science Foundation of Shanghai (No. 12ZR1410500) (No. 12ZR1410500)

Amino acids were found to be as good ligands for copper-catalyzed borylation reactions of primary and secondary alkyl halides, and the B₂pin₂ acted as bi-boron source for borylation. The high reaction efficiency and mild conditions make the new catalyst system a useful alternative to the recently developed methods for the preparation of alkylboronic esters.
- Cu-catalyzed,
- Borylation,
- Amino acid,
- Alkylboronic,
- Organoboron
1. [1]
  [1] T.C. Atack, R.M. Lecker, A.P. Cook, Iron-catalyzed borylation of alkyl electrophiles, J. Am. Chem. Soc. 136 (2014) 9521-9523.
2. [2]
  [2] (a) P.J. Unsworth, D. Leonori, V.K. Aggarwal, Stereocontrolled synthesis of 1,5-stereogenic centers through three-carbon homologation of boronic esters, Angew. Chem. Int. Ed. 53 (2014) 9846-9850; (b) K.L. Billingsley, T.E. Barder, S.L. Buchwald, Palladium-catalyzed borylation of aryl chlorides: scope, applications, and computational studies, Angew. Chem. 119 (2007) 5455-5459; (c) M.A. Larsen, J.F. Hartwig, Iridium-catalyzed C-H borylation of heteroarenes: scope, regioselectivity, application to late-stage functionalization, and mechanism, J. Am. Chem. Soc. 136 (2014) 4287-4299; (d) C.W. Liskey, J.F. Hartwig, Iridium-catalyzed C-H borylation of cyclopropanes, J. Am. Chem. Soc. 135 (2013) 3375-3378; (e) L.S. Zhang, G.H. Chen, X. Wang, et al., Direct borylation of primary C-H bonds in functionalized molecules by palladium catalysis, Angew. Chem. 126 (2014) 3980-3984; (f) J. Yu, L. Zhang, G.B. Yan, Metal-free, visible light-induced borylation of aryldiazonium salts: a simple and green synthetic route to arylboronates, Adv. Synth. Catal. 354 (2012) 2625-2628; (g) 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; (h) G.B. Yan, Y.B. Jiang, C.X. Kuang, et al., Nano-Fe₂O₃-catalyzed direct borylation of arenes, Chem. Commun. 46 (2010) 3170-3172.
3. [3]
  [3] For selected work on the copper-catalyzed reactions, see: (a) X. Zhang, H. Yi, Z.X. Liao, et al., Copper-catalysed direct radical alkenylation of alkyl bromides, Org. Biomol. Chem. 12 (2014) 6790-6793; (b) X.Y. Li, B.J. Li, J.S. You, J.B. Lan, Copper-catalysed oxidative C-H/N-H crosscoupling between formamides and amides through chelation-assisted N-H activation, Org. Biomol. Chem. 11 (2013) 1925-1928; (c) 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.
4. [4]
  [4] N. Miyaura, A. Suzuki, Palladium-catalyzed cross-coupling reactions of organoboron compounds, Chem. Rev. 95 (1995) 2457-2483.
5. [5]
  [5] C.T. Yang, Z.Q. Zhang, H. Tajuddin, et al., Alkylboronic esters from copper-catalyzed borylation of primary and secondary alkyl halides and pseudohalides, Angew. Chem. Int. Ed. 51 (2012) 528-532.
6. [6]
  [6] (a) W. Deng, Y.F. Wang, Y. Zou, L. Liu, Q.X. Guo, Amino acid-mediated Goldberg reactions between amides andaryl iodides, Tetrahedron Lett.45 (2004) 2311-2315; (b) W. Deng, Y. Zou, Y.F. Wang, L. Liu, Q.X. Guo, CuI-catalyzed coupling reactions of aryl iodides and bromides with thiols promoted by amino acid ligands, Synlett (2004) 1254-1258; (c) W. Deng, L. Liu, C. Zhang, M. Liu, Q.X. Guo, Copper-catalyzed cross-coupling of sulfonamides with aryl iodides and bromides facilitated by amino acid ligands, Tetrahedron Lett. 46 (2005) 7295-7298; (d) X. Cui, Z. Li, C.Z. Tao, et al., N,N-dimethyl-b-alanine as an inexpensive and efficient ligand for palladium-catalyzed Heck reaction, Org. Lett. 8 (2006) 2467-2470; (e) X. Cui, J. Li, Z.P. Zhang, et al., Pd(quinoline-8-carboxylate)2 as a low-priced, phosphine-free catalyst for Heck and Suzuki reactions, J. Org. Chem. 72 (2007) 9342-9345.
7. [7]
  [7] C. Kleeberg, Z.Y. Lin, T.B. Marder, A facile route to aryl boronates: room-temperature, copper-catalyzed borylation of aryl halides with alkoxy diboron reagents, Angew. Chem. 121 (2009) 5454-5458.
8. [8]
  [8] For selected work on amino acids and their derivatives as ligands in synthetic organic chemistry, see: (a) D.W. Ma, Q. Cai, Copper/amino acid catalyzed cross-couplings of aryl and vinyl halides with nucleophiles, Acc. Chem. Res. 41 (2008) 1450-1460; (b) D.W. Ma, Q. Cai, H. Zhang, Mild method for Ullmann coupling reaction of amines and aryl halides, Org. Lett. 5 (2003) 2453-2455; (c) J.S. Zheng, H.N. Chang, F.L. Wang, L. Liu, Fmoc synthesis of peptide thioesters without post-chain-assembly manipulation, J. Am. Chem. Soc. 133 (2011) 11080-11083; (d) S. Gladiali, E. Alberico, Asymmetric transfer hydrogenation: chiral ligands and applications, Chem. Soc. Rev. 35 (2006) 226-236; (e) C.T. Yang, Y. Fu, Y.B. Huang, et al., Room-temperature copper-catalyzed carbon-nitrogen coupling of aryl iodides and bromides promoted by organic ionic bases, Angew. Chem. Int. Ed. 48 (2009) 7398-7401.
9. [9]
  [9] For selected work on boryllithium, see: (a) Y. Segawa, Y. Suzuki, M. Yamashita, K. Nozaki, Chemistry of boryllithium: synthesis, structure, and reactivity, J. Am. Chem. Soc. 130 (2008) 16069-16079; (b) P. Jaramillo, P. Pérez, P. Fuentealba, Chemical reactivity descriptors for ambiphilic reagents: dual descriptor, local hypersoftness, and electrostatic potentia, J. Phys. Chem. A 113 (2009) 6812-6817; (c) K. Nozaki, Y. Aramaki, M. Yamashita, S.H. Ueng, M.M. Curran, Boryltrihydroborate: synthesis, structure, and reactivity as a reductant in ionic, organometallic, and radical reactions, J. Am. Chem. Soc. 132 (2010) 11449-11451.
10. [10]
  [10] A. Boneta, V. Lilloa, J. Ramíreza, M.M. Requejob, E. Fernández, The selective catalytic formation of b-boryl aldehydes through a base-free approach, Org. Biomol. Chem. 7 (2009) 1533-1535.
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