Construction of multiple, contiguous quaternary stereocenters in acyclic molecules by lithiation-borylation

Charlotte G. Watson, Angelica Balanta, Tim G. Elford, Stéphanie Essafi, Jeremy N. Harvey*, Varinder K. Aggarwal

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

49 Citations (Scopus)

Abstract

Lithiation of carbamates followed by borylation provides a powerful method for the homologation of boron reagents. However, when applied to hindered systems (secondary carbamates with tBu-boronic esters) for the construction of two quaternary centers, this methodology fails. Instead, using mixed boranes (tBuBMe2), the synthesis of adjacent quaternary stereogenic centers with full stereocontrol was successful. The process can be repeated two or three times in one pot leading to carbon chains bearing multiple contiguous quaternary stereogenic centers. The boranes were converted into tertiary alcohols or C-tertiary amines using chloramine. The origin of the high selectivity for alkyl over Me group migration was determined computationally.

Original languageEnglish
Pages (from-to)17370-17373
Number of pages4
JournalJournal of the American Chemical Society
Volume136
Issue number50
DOIs
Publication statusPublished - 17 Dec 2014

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