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Carbenoid

From Wikipedia, the free encyclopedia

Inchemistry acarbenoid is areactive intermediate that shares reaction characteristics with acarbene.[1] In theSimmons–Smith reaction the carbenoid intermediate is azinc /iodinecomplex that takes the form of

I-CH2-Zn-I

This complex reacts with analkene to form acyclopropane just as a carbene would do.

Carbenoids appear as intermediates in many other reactions. In one system a carbenoid chloroalkyllithium reagent is prepared in situ from asulfoxide andt-BuLi which reacts the boronic ester to give an ate complex. The ate complex undergoes a 1,2-metallate rearrangement to give the homologated product, which is then further oxidised to a secondary alcohol.[2]

Insertion of carbenoid into C-B bond

Theenantiopurity of the chiral sulfoxide is preserved in the ultimate product after oxidation of the boronic ester to thealcohol indicating that a true carbene was never involved in the sequence.

See also

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References

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  1. ^Organic Chemistry john McMurry Brooks /Cole Publishing Company 1988ISBN 0-534-07968-7
  2. ^Iterative Stereospecific Reagent-Controlled Homologation of Pinacol Boronates by Enantioenriched -Chloroalkyllithium Reagents Paul R. Blakemore and Matthew S. BurgeJ. Am. Chem. Soc.;2007; 129(11) pp 3068 - 3069; (Communication)doi:10.1021/ja068808s
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