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Volumn 121, Issue 5, 1999, Pages 949-957

Stereospecific and regioselective reactions of silacyclopropanes with carbonyl compounds catalyzed by copper salts: Evidence for a transmetalation mechanism

Author keywords

[No Author keywords available]

Indexed keywords

COPPER; CYCLOPROPANE;

EID: 0033540626     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja982897u     Document Type: Article
Times cited : (58)

References (68)
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    • This formamide was used to simplify spectral analyses.
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    • note
    • 1H NMR spectroscopy is most likely due to the presence of trans-2-butene as an impurity in commercially available cis-2-butene, from which silacyclopropane cis-1 was made. The typical purity of cis-1 is ≥95%.
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    • note
    • The stereochemistry of these products was proven rigorously. The details are provided as Supporting Information.
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    • note
    • The stereochemistries of insertion products derived from 8 were determined by analysis of NOE data. A summary of these data is provided as Supporting Information.
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    • Bleaching of the characteristic blue-green color of copper(II) salts was observed upon addition of the silacyclopropane. The reduction of palladium(II) salts with silacyclopropanes was demonstrated: Seyferth, D.; Shannon, M. L.; Vick, S. C.; Lim, T. F. O. Organometallics 1985, 4, 57-62.
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    • Use of 10 mol % CuI with crotonaldehyde led to a 64% yield of 10b as an 87:13 mixture of diastereomers; ZnBr2 afforded a 62% yield of an 87:13 mixture. An 87:13 mixture was observed for CuI-catalyzed insertion of tiglic aldehyde. These mixtures permitted comparison of NOE data between the major and minor diastereomers.
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    • The stereochemistry of 18a was determined unambiguously (ref 5). The stereochemistries of 18b-d were assigned by analogy.
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    • For some examples of the stereochemistry of transmetalation reactions, see: (a) Silicon to palladium: Hatanaka, Y.; Hiyama, T. J. Am. Chem. Soc. 1990, 112, 7793-7794. (b) Tin to copper: Falck, J. R.; Bhatt, R. K.; Ye, J. J. Am. Chem. Soc. 1995, 117, 5973-5982. Boron to palladium: Ridgway, B. H.; Woerpel, K. A. J. Org. Chem. 1998, 68, 458- 460. Matos, K.; Soderquist, J. A. J. Org. Chem. 1998, 63, 461-470.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.