Alkoxide-Assisted Stereoselective Functionalization of 1,2-Bis-boronic Esters Under Photoredox Catalysis.

Site-specific functionalization of the secondary C-B bond of 1,2-bis-boronic esters has been proven to be an important method for the generation of 1,2-bis-functionalized compounds in a highly stereoselective manner. We have explored previously unknown secondary selective alkenylation, allylation, alkynylation and addition to aryl vinyl trifluoromethane, which proceeds via a novel reaction mechanism: alkoxide-mediated photoredox activation to generate secondary radicals over the primary one.

Transition-Metal-Free Heterocyclic Carbon-Boron Bond Formation.

Heteroaryl boronic acids and esters are extremely important and valuable intermediates because of their wide application in the synthesis of marketed drugs and bioactive compounds. Over the last couple of decades, the construction of highly important heteroaryl carbon-boron bonds has created huge attention. The transition-metal-free protocols are more green, less sensitive to air and moisture, and also economically advantageous over the transition-metal-based protocols. The transition-metal-free C-H borylation of heteroarenes and C-X (X=halogen) borylation of heteroaryl halides represents an excellent approach for their synthesis. Also, various cyclization and alkyne activation protocols have been recently established for their synthesis. The goal of this review article is to summarize the existing literature and the current state of the art for transition-metal-free synthesis of heteroaryl boronic acid and esters.

Development of Methods to the Synthesis of ß-Boryl Acyls, Imines and Nitriles.

Organoboron compounds are highly important and versatile synthetic intermediates for the preparation of a wide range of organic molecules. Organoboron compounds have drawn significant attention among organic chemists due to their Lewis acidic property, non-toxicity, and commercial availability. Over the last several decades, there has been a substantial development of new organoboron compounds, useful in organic synthesis. Among all other organoboron compounds, ß-boryl carbonyl compounds are the important ones. The ß-boryl compounds have appeared as promising intermediates for various synthetic transformations. The 1,4-conjugate addition of diboron reagents to carbon-carbon double bond in the presence of different transition-metal catalysts has been extensively reported by various research groups across the globe. This mini-review outlines the numerous racemic as well as asymmetric ß-borylation methods developed to date.