Copper-mediated cross-coupling of functionalized arylmagnesium reagents with functionalized alkyl and benzylic halides

Organic Letters

Volumn 3, Issue 18, 2001, Pages 2871-2873

  Dohle, Wolfgang ^a   Lindsay, David M ^a   Knochel, Paul ^a  

^a UNIVERSITY OF MUNICH   (Germany)

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ARTICLE;

EID: 0000985581     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0163272     Document Type: Article

References (25)

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2. (b) Tamao, K. Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Pattenden, G., Eds.; Pergamon: Oxford, 1991; Vol. 3, Chapter 2.2, p 435.
3. (a) Rottländer, M.; Boymond, L.; Bérillon, L.; Leprêtre, A.; Varchi, G.; Avolio, S.; Laaziri, H.; Quéguiner, G.; Ricci, A.; Cahiez, G.; Knochel, P. Chem. Eur. J. 2000, 6, 767.
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9. For Cu(I)-catalyzed cross-coupling between functionalized zinc reagents and alkyl iodides, see: Tucker, C. E.; Knochel, P. J. Org. Chem. 1993, 58, 4781.
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18. The commercially available isopropylmagnesium chloride (either as a solution in THF or diethyl ether) is equally suitable for the halogen-magnesium exchange.
19. Addition of DMPU or NMP as a cosolvent offers no significant improvement in the rate or yield of the exchange or cross-coupling. When diethyl ether is used as solvent, addition to any reactive functional group (e.g., ester) is observed instead of I-Mg exchange.
20. Knochel, P.; Yeh, M. C. P.; Berk, S. C.; Talbert, J. J. Org. Chem. 1988, 53, 2390.
21. Alkyl tosylates do not undergo the reaction.
22. In the absence of any Cu species, the reaction proceeds in very low yield. For example, the cross-coupling between 1a and 2a gave product 4a in only 6% yield after 72 h at -5°C.
23. Masada, H.; Yasunishi, Y.; Kikuchi, N. Nippon Kagaku Kaishi 1995, 10, 844.
24. 2 (20 mol %), the expected product 4a was formed in only 20% yield (compared with 60% with CuCN·2LiCl). When Cu(OAc) (20 mol %) was employed as the catalyst, arylmagnesium species 1a and iodide 2c were coupled to give 4c in 46% yield (compared with 57% using CuCN· 2LiCl).
25. 2) to give 288 mg of a colorless oil (63% yield).