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Volumn 62, Issue 10, 1997, Pages 3315-3323

Rh(II)-Catalyzed Reaction of Some α′,α′- and β′-Branched-O-Alkyl α-(Alkoxycarbonyl)-α-diazoacetates

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EID: 1542608055     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo961484d     Document Type: Article
Times cited : (1)

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    • See Supporting Information
    • See Supporting Information.
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    • For discussion on the dramatic influence of solvent polarity on the chemoselectivity of the Rh(II) carbenoid-mediated reaction, see (a) Davies, H. M. L.; Matasi, J. J.; Ahmed, G. J. Org. Chem. 1996, 61, 2305. (b) Davies, H. M. L.; Saikali, E.; Young, W. B. J. Org. Chem. 1991, 56, 5696 and references cited therein.
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    • 4 favored insertion into tertiary C-H bond
    • 4 favored insertion into tertiary C-H bond,
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    • 4 was also found to favor cyclopropanation reaction, see (i) Sundberg, R. J.; Baxter, E. W.; Pitts, W. J.; Ahmed-Schofield, R.; Nishiguchi, T. J. Org. Chem. 1988, 53, 5097. (ii) Anciaux, A. J.; Hubert, A. J.; Noels, A. F.; Petiniot, N.; Teyssie, P. J. Org. Chem. 1980, 45, 695. (iii) Hubert, A. J.; Noels, A. F.; Anciaux, A. J.; Teyssie, P. Synthesis 1976, 600.
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    • 4 was also found to favor cyclopropanation reaction, see (i) Sundberg, R. J.; Baxter, E. W.; Pitts, W. J.; Ahmed-Schofield, R.; Nishiguchi, T. J. Org. Chem. 1988, 53, 5097. (ii) Anciaux, A. J.; Hubert, A. J.; Noels, A. F.; Petiniot, N.; Teyssie, P. J. Org. Chem. 1980, 45, 695. (iii) Hubert, A. J.; Noels, A. F.; Anciaux, A. J.; Teyssie, P. Synthesis 1976, 600.
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    • note
    • Diazo compounds in which the ethyl group in 2a,b was replaced with a 3,4-dimethoxyphenyl moiety were also prepared. The Rh(II)-catalyzed reaction in 2a resulted in an intractable mixture of products whereas in 2b there was a marked decrease in the regio- and chemoselectivities of the reaction. A complex mixture of products, such as those that had resulted from tertiary C-H insertion, aromatic substitution and cycloaddition, were obtained.
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