Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 142, Issue 12, Pages 5515-5520Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.0c00813
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Funding
- EU [840000]
- Bristol Chemical Synthesis Centre for Doctoral Training, EPSRC [EP/G036764/1]
- UCB
- University of Bristol [EP/R513179/1]
- Marie Curie Actions (MSCA) [840000] Funding Source: Marie Curie Actions (MSCA)
- EPSRC [EP/L011999/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/L011999/1] Funding Source: researchfish
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The broad synthetic utility of organoboron compounds stems from their ready ability to undergo 1,2-migrations. Normally, such shifts are induced by alpha-leaving groups or by reactions of alkenyl boronates with electrophiles. Herein, we present a new strategy to induce 1,2-metalate rearrangements, via ring expansion of vinylcyclopropyl boronate complexes activated by electrophiles. This leads to a cyclopropane-stabilized carbocation, which triggers ring expansion and concomitant 1,2-metalate rearrangement. This novel process delivers medicinally relevant 1,2-substituted cyclobutyl boronic esters with high levels of diastereoselectivity. A wide range of organolithiums and Grignard reagents, electrophiles, and vinylcyclopropyl boronic esters can be used. The methodology was applied to a short, stereoselective synthesis of (+/-)-grandisol. Computational studies indicate that the reaction proceeds via a nonclassical carbocation followed by anti-1,2-migration.
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