Abstract
AbstractThe stereospecific 1,2‐migration of boronate complexes is one of the most representative reactions in boron chemistry. This process has been used extensively to develop powerful methods for asymmetric synthesis, with applications spanning from pharmaceuticals to natural products. Typically, 1,2‐migration of boronate complexes is driven by displacement of an α‐leaving group, oxidation of an α‐boryl radical, or electrophilic activation of an alkenyl boronate complex. The aim of this article is to summarize the recent advances in the rapidly expanding field of electrophile‐induced stereospecific 1,2‐migration of groups from boron to sp2 and sp3 carbon centers. It will be shown that three different conceptual approaches can be utilized to enable the 1,2‐migration of boronate complexes: stereospecific Zweifel‐type reactions, catalytic conjunctive coupling reactions, and transition metal‐free sp2–sp3 couplings. A discussion of the reaction scope, mechanistic insights, and synthetic applications of the work described is also presented.
Highlights
The stereospecific 1,2-migration of boronate complexes is one of the most representative reactions in boron chemistry
Stereospecific 1,2-Migration of Alkenyl Boronates Induced by Electrophiles synthesis, with applications spanning from pharmaceuticals to natural 2.1
1,2-migration of boronate complexes is driven by displacement of an a-leaving group, oxidation of an a-boryl radical, or electrophilic activation of an alkenyl boronate complex
Summary
In 2017, Aggarwal reported a modified Zweifel-type olefination proceeding through a novel syn elimination process (Scheme 9).[27] This was achieved by employing PhSeCl as the electrophile for the selenation of alkenyl boronates 43, which led to b-selenoboronic esters 46 through the stereospecific 1,2-migration ring-opening of seleniranium intermediates 45. Lewis base-catalyzed enantioselective electrophile-induced 1,2-migration of alkenyl boronates. A source of electrophilic sulfur, an enantioselective sulfenylation was achieved. This provided access to a broad array of enantioenriched anti b-sulfenoboronic esters 50 with two contiguous stereogenic centers with complete diastereoselectivity. Reaction of 52 with alkenyl boronate 48 generates the enantioenriched thiiranium ion 49, which undergoes 1,2-migration to generate anti-products 50 with high enantioselectivity
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