First-Row d-Block Element-Catalyzed Carbon–Boron Bond Formation and Related Processes

Abstract

Organoboron reagents represent a unique class of compounds because of their utility in modern synthetic organic chemistry, often affording unprecedented reactivity. The transformation of the carbon−boron bond into a carbon−X (X = C, N, and O) bond in a stereocontrolled fashion has become invaluable in medicinal chemistry, agrochemistry, and natural products chemistry as well as materials science. Over the past decade, first-row dblock transition metals have become increasingly widely used as catalysts for the formation of a carbon−boron bond, a transformation traditionally catalyzed by expensive precious metals. This recent focus on alternative transition metals has enabled growth in fundamental methods in organoboron chemistry. This review surveys the current state-of-the-art in the use of first-row d-block element-based catalysts for the formation of carbon−boron bonds.

Primary trifluoroborate-iminiums enable facile access to chiral α-aminoboronic acids via Ru-catalyzed asymmetric hydrogenation and simple hydrolysis of the trifluoroborate moiety

“…Organoboron compounds 1 play a pivotal role in synthetic organic chemistry, where they have enabled a myriad of useful transformations 2–4 and have also been used in the field of materials science. 5 The most advantageous application of organoboron compounds was achieved in medicinal chemistry 6 where several boron-containing drugs reached the market in the last two decades.…”

Modern Development in Copper‐ and Nickel‐Catalyzed Cross‐Coupling Reactions: Formation of Carbon‐Carbon and Carbon‐Heteroatom bonds under Microwave Irradiation Conditions

“…These devices can accomodate several rotor types for parallel reactions in a vessel volume up to 100 mL. [30][31][32][33] Although the chemical literature provides a valuable number of reviews on copper-and nickel-catalyzed reactions, [34][35][36][37] this review article critically focuses the attention on the recent progress on copper-and nickel-catalyzed cross-coupling reactions using various metal catalysts under distinctive attributes of microwave heating reported during the last decade. It highlights as well on the more stable and sustainable metal catalysts used; the improvement and intensification of reaction selectivity are symbolizing the current challenges in order to reach to the well-established activity level of palladium catalysts.…”

Organosuperbase Catalyzed 1,1-Diboration of Alkynes

“…Organoboron compounds are unarguably one of the most valuable families of synthetic building blocks in organic chemistry. [1][2][3][4][5] Multiboronate precursors have recently attracted immense attention from synthetic chemists due to their versatile and tunable reactivity, especially in the cross-coupling chemistry that leads to a plethora of organic structures, bioactive compounds and advanced functional materials. 6,7 Diborylalkenes are probably the most utilized synthetic precursors in this sub-class, as they offer distinctive pathways to the construction of multi-substituted alkenes in regio-or stereoselective manner.…”

“…In the pursuit of an organocatalytic system that is capable of promoting the diboration reaction of terminal alkynes in a similar fashion, we envision that this new catalyst should have strong Brønsted basicity to break the weakly acidic C(sp)-H bond. It should also possess either strong p-Lewis acidity 5 to activate the C-C triple bond or s-Lewis basicity to activate the boron reagent. [1][2][3][4] The former feature is incompatible with the desired Brønsted basicity, so it has to be the latter.…”