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DOI: 10.1055/s-0035-1562096
Stereoselective Synthesis of Secondary Alkyllithiums and Their Application to Stereoselective Cuprations or Intramolecular Carbolithiations for the Stereoselective Synthesis of Alkylidenecyclobutanes
Publikationsverlauf
Received: 08. März 2016
Accepted after revision: 04. April 2016
Publikationsdatum:
23. Mai 2016 (online)
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Dedicated with great respect and admiration to Professor Jean F. Normant on the occasion of his 80th birthday and in recognition of his pioneering contributions to organometallic chemistry
Abstract
Secondary alkyllithium reagents were prepared stereoselectively via an iodo–lithium exchange by using tert-butyllithium. The resulting secondary alkyllithiums were converted directly into the corresponding alkylcopper reagents by transmetalation with copper(I) bromide–triethyl phosphite [CuBr·P(OEt)3] with retention of configuration and without significant loss of stereoselectivity. The resulting alkylcopper reagents were used for carbocupration or acylation reactions. In addition, a new intramolecular carbolithiation of secondary alkyllithium reagents possessing a remote alkyne moiety was also investigated, allowing the stereoselective production of alkylidenecylobutane derivatives with very high stereocontrol.
Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0035-1562096.
- Supporting Information
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Recent examples:
Transmetalation of heteroatom-stabilized alkyllithiums to alkylcopper reagents:
Other carbocuprations:
Intramolecular carbolithiation:
Spirocyclobutane bearing an epoxide: