Alkylation boron stabilized carbanions

In general, all types of boron-stabilized carbanions are readily alkylated by primary alkyl halides. The situation for the i ylation of dimesitylboryl compounds is sununarized in Scheme 2. These reactions represent highly efficient homologation processes. Oxidation of the tertiary all l organoboranes is slow, but use of 4-methoxy-2,6-dimethylphenyl groups instead of mesityl groups renders the products sensitive to solvolysis. ... 

Alkylations of boron-stabilized carbanions have been carried out with primary alkyl halides containing acetal, alkene, alkyne, chloride, cyano, ester and tosylate groups, though a ketone group was not tolerated. ... 

Rathice and Kow first reported the preparation of a boron-stabilized carbanion by direct deprotonation of the carbon acid. They made the important observation that the deprotonation needed a sterically demanding base to prevent its complexation with boron. Thus the anion of B-methyl-9-borabicy-clo[3.3.1]nonane, prepared by deprotonation with lithium 2,2,6,6-tetramethylpiperidine (LiTMP) in benzene, can be alkylated successfully. 

Matteson and coworkers have described the deprotonation and alkylation of bis(l,3,2-dioxaborin-2-yOmethane (11). Deprotonation with LiTMP yields the stabilized anion, which can be alkylated with a variety of primary alkyl halides. Oxidation under basic conditions then unmasks the carbonyl group. Matteson has also described the deprotonation of some substituted boronic esters (12 X = SPh, SiMei). - The alkylated products derived from (12 X = SPh) can be treated with A/-chlorosuccinimide under mild basic conditions to yield either the monothioacetals or the acetals. Boron-stabilized carbanions can also be generated by transmetallation of the organostannanes. ... 

Corey et al have elegantly exploited the ability of oxime ethers to stabilize carbanions syn to the N-alkoxy substituent in the boron trifluoride mediated addition of the mixed cuprate reagent derived from (177) to a,3-unsaturated oxime ether (178 Scheme 34). Stereochemistry is established by the ring r-bu-tyldimethylsiloxy group. The addition does not occur in the absence of boron tiifluoride. The alkylation of the cuprate adduct of (178) by iodoalkyne (179) provides the PGEj skeleton. 

A treatment of 314 with LDA yielded a carbanion stabilized by boron and sulfur atom, which undergoes alkylation with organic halides and with methyl acrylate (Equation (93)).473... 

This chapter deals with the formation of new C—C bonds by alkylation of sp -hybridized carbanions stabilized by a range of heteroatoms, including oxygen, boron, silicon, phosphorus and the halogens. The properties of the same carbanions with additional stabilization provided by an adjacent double bond are also discussed. 

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