Hiyama reactions of activated and unactivated secondary alkyl halides catalyzed by a nickel/norephedrine complex

Angewandte Chemie - International Edition

Volumn 46, Issue 19, 2007, Pages 3556-3558

  Strotman, Neil A ^a   Sommer, Stefan ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

Amino alcohols; Cross coupling; Homogeneous catalysis; Nickel; Silicon

Indexed keywords

ALKALINITY; AMINES; CATALYST ACTIVITY; NICKEL COMPOUNDS; REACTION KINETICS;

AMINO ALCOHOLS; CROSS-COUPLING; HIYAMA CROSS-COUPLING REACTIONS; HOMOGENEOUS CATALYSIS;

HALIDE MINERALS;

EID: 34250821753     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200700440     Document Type: Article

References (29)

1. For reviews of the Hiyama reaction, see: a) S. E. Denmark, R. F. Sweis in Metal-Catalyzed Cross-Coupling Reactions (Eds.: A. de Meijere, F. Diederich), Wiley-VCH, New York, 2004, chap. 4;
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16. 2·glyme or of norephedrine, no cross-coupling was observed;
17. b) the Hiyama reaction proceeded best at high concentrations (0.5 M);
18. 2O, but less efficiently; the origin of this water (or hydroxide) effect is not yet clear.
19. Bathophenanthroline proved to be ineffective (<5% yield).
20. a) In preliminary experiments under our standard conditions, Hiyama cross-coupling reactions of hindered unactivated secondary bromides, unactivated secondary chlorides, and primary halides have not been efficient (<50% yield). We have not yet explored the capacity of other nickel/amino alcohol catalysts to achieve Hiyama reactions of these families of substrates;
21. b) we can efficiently cross-couple an unactivated secondary alkyl bromide (>80% yield) in the presence of an unactivated secondary alkyl chloride (<2% yield).
22. 3, 1.44 g (81%));
23. rel > 50) of an activated secondary bromide (ethyl 2-bromoisovalerate) in the presence of an unactivated secondary bromide (cyclohexyl bromide);
24. c) a preliminary study indicates that benzylic halides are not useful cross-coupling partners under our standard conditions.
25. To the best of our knowledge, no examples of nickel- or palladium-catalyzed cross-coupling reactions of secondary α-halocarbonyl compounds with aryl metal reagents (for example, boron, silicon, tin, and zinc) have been described; couplings of primary α-halocarbonyl compounds appear to be limited to Suzuki reactions; for examples, see: a) M. Sato, N. Miyaura, A. Suzuki, Chem. Lett. 1989, 1405-1408;
26. b) L. J. Goossen, Chem. Commun. 2001, 669-670;
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