Synthesis 2013; 45(4): 518-526
DOI: 10.1055/s-0032-1316841
paper
© Georg Thieme Verlag Stuttgart · New York

Dilithium Tetrachlorocuprate(II) Catalyzed Oxidative Homocoupling of Functionalized Grignard Reagents

Si-Kai Hua
b   Shanghai Key Laboratory of Chemical Biology, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. of China   Fax: +86(21)64253689   Email: renjm@ecust.edu.cn   Email: zengbb@ecust.edu.cn
,
Qiu-Peng Hu
b   Shanghai Key Laboratory of Chemical Biology, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. of China   Fax: +86(21)64253689   Email: renjm@ecust.edu.cn   Email: zengbb@ecust.edu.cn
,
Jiangmeng Ren*
b   Shanghai Key Laboratory of Chemical Biology, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. of China   Fax: +86(21)64253689   Email: renjm@ecust.edu.cn   Email: zengbb@ecust.edu.cn
,
Bu-Bing Zeng*
a   Shanghai Key Laboratory of New Drug Design, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. of China
b   Shanghai Key Laboratory of Chemical Biology, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. of China   Fax: +86(21)64253689   Email: renjm@ecust.edu.cn   Email: zengbb@ecust.edu.cn
› Author Affiliations
Further Information

Publication History

Received: 24 September 2012

Accepted after revision: 16 December 2012

Publication Date:
10 January 2013 (online)


Abstract

An efficient procedure is described for the oxidative homocoupling of functionalized Grignard reagents using a catalytic amount of dilithium tetrachlorocuprate(II) (CuLi2Cl4) in the presence of pure oxygen gas. This method is applied successfully to a variety of aryl, heteroaryl, alkyl, alkenyl and alkynyl halides, which are converted into the corresponding homocoupled products in good to excellent yields.

Supporting Information

 
  • References

    • 1a Inoue A, Kitagawa K, Shinokubo H, Oshima K. Tetrahedron 2000; 56: 9601
    • 1b McKillop A, Elsom LF, Taylor EC. J. Am. Chem. Soc. 1968; 90: 2423
    • 1c Ishikawa T, Ogawa A, Hirao T. Organometallics 1998; 17: 5713
    • 1d Hirao T. Coord. Chem. Rev. 2003; 237: 271
    • 1e Nagano T, Hayashi T. Org. Lett. 2005; 7: 491
    • 1f Cahiez G, Moyeux A, Buendia J, Duplais C. J. Am. Chem. Soc. 2007; 129: 13788
    • 1g Hatakeyama T, Hashimoto S, Ishizuka K, Nakamura M. J. Am. Chem. Soc. 2009; 131: 11949
    • 1h Cahiez G, Chaboche C, Mahuteau-Betzer F, Ahr M. Org. Lett. 2005; 7: 1943
    • 1i Liu W, Lei A. Tetrahedron Lett. 2008; 49: 610
    • 1j Kude K, Hayase S, Kawatsura M, Itoh T. Heteroat. Chem. 2011; 22: 397
    • 1k Kharasch MS, Fields EK. J. Am. Chem. Soc. 1941; 63: 2316
    • 1l Chen S.-Y, Zhang J, Li Y.-H, Wen J, Bian S.-Q, Yu X.-Q. Tetrahedron Lett. 2009; 50: 6795
    • 1m Surry DS, Su X, Fox DJ, Franckevicius V, Macdonald SJ. F, Spring DR. Angew. Chem. Int. Ed. 2005; 44: 1870
    • 1n Yuan Y, Bian Y. Appl. Organomet. Chem. 2008; 22: 15
    • 1o Zhou Z, Xue W. J. Organomet. Chem. 2009; 694: 599
    • 1p Kanth SR, Reddy GV, Yakaiah T, Narsaiah B, Rao PS. Synth. Commun. 2006; 36: 3079
    • 1q Moglie Y, Mascaró E, Nador F, Vitale C, Radivoy G. Synth. Commun. 2008; 38: 3861
    • 2a Transition Metals for Organic Synthesis . Vol. 1. Beller M, Bohm C. Wiley-VCH; New York: 1998
    • 2b Metal-Catalyzed Cross-Coupling Reactions . Diedrich F, Stang PJ. Wiley-VCH; Weinheim: 1998
    • 2c Beller M, Zapf A, Magerlein W. Chem. Eng. Technol. 2001; 24: 575
    • 2d Handbook of Combinatorial Chemistry: Drugs, Catalysts, Materials . Nicolaou KC, Hanko R, Hartwig W. Wiley-VCH; Weinheim: 2002
  • 3 For an excellent overview of the use of dilithium tetrachlorocuprate(II) in organic synthesis, see: Thompson AS, Kim JT, Gevorgyan V. e-EROS, Encyclopedia of Reagents for Organic Synthesis . John Wiley & Sons; New York: 2004. DOI: doi: 10.1002/047084289X.rd268.pub2
    • 4a Iyoda M. Adv. Synth. Catal. 2009; 351: 984
    • 4b Kochi JK. J. Organomet. Chem. 2002; 653: 11
    • 4c Kauffmann T. Angew. Chem., Int. Ed. Engl. 1974; 13: 291
    • 4d Miyake Y, Wu M, Rahman MJ, Kuwatani Y, Iyoda M. J. Org. Chem. 2006; 71: 6110
    • 4e Dubbaka SR, Kienle M, Mayr H, Knochel P. Angew. Chem. Int. Ed. 2007; 46: 9093
    • 5a Bäckvall J.-E, Sellén M. J. Chem. Soc., Chem. Commun. 1987; 827
    • 5b Kochi JK. Organometallic Mechanisms and Catalysis . Academic Press; New York: 1978: 381
    • 6a Krasovskiy A, Knochel P. Angew. Chem. Int. Ed. 2004; 43: 3333
    • 6b Hatano M, Ito O, Suzuki S, Ishihara K. J. Org. Chem. 2010; 75: 5008
  • 7 Frisch AC, Beller M. Angew. Chem. Int. Ed. 2005; 44: 674
    • 8a Varchi G, Ricci A, Cahiez G, Knochel P. Tetrahedron 2000; 56: 2727
    • 8b Sapountzis I, Knochel P. Angew. Chem. Int. Ed. 2002; 41: 1610
    • 8c Knochel P, Dohle W, Gommermann N, Kneisel FF, Kopp F, Korn T, Sapountzis I, Vu VA. Angew. Chem. Int. Ed. 2003; 42: 4302
    • 9a Pradilla RF, Lwoff N, Águila MÁ, Tortosa M, Viso A. J. Org. Chem. 2008; 73: 8929
    • 9b Miranda LD, Zard SZ. Org. Lett. 2002; 4: 1135
  • 10 All of the homocoupling reactions were conducted on 3 mmol scale. The present system was also scaled 10-fold for compounds 1b and 20b; these reactions proceeded efficiently and no problems were encountered.
  • 11 Periasamy M, Nagaraju M, Kishorebabu N. Synthesis 2007; 3821
  • 12 Nishimura N, Yoza K, Kobayashi K. J. Am. Chem. Soc. 2010; 132: 777
  • 13 Jaworek W, Vögtle F. Chem. Ber. 1991; 124: 347
  • 14 Hertzog-Ronen C, Borzin E, Gerchikov Y, Tessler N, Eichen Y. Chem. Eur. J. 2009; 15: 10380
  • 15 Case FH. J. Am. Chem. Soc. 1946; 68: 2574
  • 16 Ribeiro PE. A, Donnici CL, dos Santos EN. J. Organomet. Chem. 2006; 691: 2037
  • 17 Verniest G, Wang X, De Kimpe N, Padwa A. J. Org. Chem. 2010; 75: 424
  • 18 Wen J.-F, Hong W, Yuan K, Mak TC. W, Wong HN. C. J. Org. Chem. 2003; 68: 8918
  • 19 Eisch JJ, Dutta S. Organometallics 2005; 24: 3355
  • 20 Lavoie J.-M, Stevanovic T. J. Agric. Food Chem. 2005; 53: 4747
  • 21 Xu X, Cheng D, Pei W. J. Org. Chem. 2006; 71: 6637
  • 22 Adimurthy S, Malakar CC, Beifuss U. J. Org. Chem. 2009; 74: 5648
  • 23 Deaton KR, Gin MS. Org. Lett. 2003; 5: 2477
  • 24 Yeung CS, Zhao XD, Borduas N, Dong VM. Chem. Sci. 2010; 1: 331