Carbonyl additions and organometallic

A. Lubineau, J. Auge, Y. Queneau, Carbonyl Additions and Organometallic Chemistry in Water in Organic Synthesis in Water (Ed. P. A. Grieco), Blacky Academic and Professional, London, 1998, pp.102-140. 

Lubineau, A., Auge, J., Queneau, Y. Carbonyl additions and organometallic chemistry in water. Organic Synthesis in Water). 1998,102-... 

The addition to the C=N bond is limited to reactive species, such as hydrogen halides, carbonyl fluoride and organometallics, and seems to proceed well only with carbonimidoyl difluorides. The dehalogenation of carbonimidoyl dihalides by triphenylphosphine provides a useful method to generate isocyanides, which are sometimes difficult to obtain by Hofmann s classical method. 

In order to understand why the notoriously water-sensitive metal-mediated reactions can proceed in water at all, it is necessary to look at three basic aspects (1) the fundamental bonding in organometallic compounds, (2) the kinetics of the hydrolysis of C—M bonds, and (3) the kinetics of carbonyl addition (and other nucleophilic reactions) by C—M bonds. 

Addition of Organometallics to Double and Triple Bonds Not Conjugated to Carbonyls... 

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