Matteson rearrangements

Laplante, C. Hall, D. G. Direct mono-N-methylation of solid-supported amino adds a useful application of the Matteson rearrangement of a-aminoalkylboronic esters. Org. Lett. 2001, 3, 1487-1490. 

PASTO-MATTESON Rearrangement Rearrangement of a-bromooiganoboranes by C migration... 

A series of silylated heterocycles using an intramolecular silicon version of the Matteson rearrangement give binuclear heterocycles via a pentaorganosilicate species (Scheme... 

The use of a Lewis acid such as zinc or ferric chloride offered an improvement to the original procedure reported by Matteson and Ray.22 Rearrangements occur at room temperature with improved conversion. Perhaps more important, the use of 0.5-1.0 equivalent ZaCh minimizes the rate of epimerization of the a-carbon center that occurs due to the presence of lithium chloride (LiCl).25 Prolonged exposure of 17 to chloride ions produced in the reaction and during the aqueous workup can decrease the stereoselectivity of the process. When complexed to ZnCl2, lithium chloride forms... 

The postulated mechanism is much akin to the cyclopropylcarbinyl rearrangements discussed earlier (Section II, D), and related to a similar process in silicon chemistry. In the boron case Matteson (193) found basicity toward boron was more important in determining the course of the reaction than nucleophlicity toward carbon. The following reactions were studied ... 

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