Site‐Selective 1,2‐Dicarbofunctionalization of Vinyl Boronates through Dual Catalysis

Abstract

A modular, site‐selective 1,2‐dicarbofunctionalization of vinyl boronates with organic halides through dual catalysis is described. This reaction proceeds under mild conditions and is characterized by excellent chemo‐ and regioselectivity. It thus represents a complementary new technique for preparing densely functionalized alkyl boron architectures from simple and accessible precursors.

Recent advances in photoredox and nickel dual-catalyzed cascade reactions: pushing the boundaries of complexity

“…Simultaneously, Martin and coworkers realized the 1,2-dicarbofunctionaliztion of vinyl boronates via the photoredox and nickel dual-catalyzed cascade cross-electrophile coupling of aryl bromides, vinyl boronates and tertiary alkyl bromides (Scheme 10). 18 This transformation provided the desired alkyl boronates in high chemo-and regioselectivity. Notably, the two-component cross-coupling products between any two coupling partners were suppressed effectively.…”

Radical Carbonyl Propargylation by Dual Catalysis

“…Since 2018, our group, [21a–c] Kanai, Mitsunuma and co‐workers [21d,e] have independently achieved allylation of aldehydes using dual photoredox and chromium catalysis [21f] . Compared to dual nickel/photoredox [20e–j] or copper/photoredox [20k–n] catalysis, dual chromium/photoredox catalytic mode is much less explored in synthetic chemistry, but provides a range of opportunities to achieve challenging radical‐to‐polar crossover‐based transformations. While alkyl chromium species could also be generated, [22] propargyl chromium species have remained out of reach by means of this emerging dual catalytic system.…”

Nickel-Catalyzed Three-Component Olefin Reductive Dicarbofunctionalization to Access Highly Functionalized Alkylborates

“…Benzylic boronates were obtained conveniently with the simultaneous formation of one aryl-alkyl bond and one alkyl-alkyl bond. 19 With respect to aryl coupling partners, both electron-donating (36) and electron-withdrawing (37-39) substituents were well tolerated in the meta-and parapositions and afforded the corresponding products in moderate (39-50%) isolated yields. In addition, this transformation is orthogonal to classical Suzuki cross-coupling procedures, as the C(sp 2 )-B bond remained intact in substrate 40.…”