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. 2009 Oct 14;131(40):14231-3.
doi: 10.1021/ja9061823.

Asymmetric carbon-carbon bond formation gamma to a carbonyl group: phosphine-catalyzed addition of nitromethane to allenes

Sean W Smith  1 , Gregory C Fu
Affiliations

Asymmetric carbon-carbon bond formation gamma to a carbonyl group: phosphine-catalyzed addition of nitromethane to allenes

Sean W Smith et al. J Am Chem Soc. .

Abstract

A chiral phosphine catalyzes the addition of a carbon nucleophile to the gamma position of an electron-poor allene (amide-, ester-, or phosphonate-substituted), in preference to isomerization to a 1,3-diene, in good ee and yield. This strategy provides an attractive method for the catalytic asymmetric gamma functionalization of carbonyl (and related) compounds.

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Figures

Figure 1
Figure 1
Possible mechanisms for phosphine-catalyzed reactions of electron-poor alkynes and allenes: Isomerization and γ addition (for the sake of simplicity, only one E/Z isomer is illustrated and all of the elementary steps are drawn as irreversible).
See this image and copyright information in PMC

References

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