Zirconium Catalyzed Transformations Using Organoboron

Abstract

Organoboron compounds have extreme potential for organic synthesis. Ready functionalization of organoboron intrigued people to develop various protocols for their synthesis. Over the last several decades, there has been a substantial development in synthesizing new organoboron compounds using transition metals. Among various transition metals, zirconium has also been found to catalyze diverse reactions of organoboron. The zirconium chemistry has become more popular with the development of zirconium metallocenes, particularly bis(cyclopentadienyl)zirconocene chloride hydride, the wellknown Schwartz reagent. These zirconium metallocenes possess a significant role in hydrozirconation, hydroboration, hydrogenation, carbozirconation, and a promising tri-n-butyl tin hydride alternative. This minireview focuses on the various transformations of organoboron employing zirconium catalysts that have been developed so far.

Progress in the Electrochemical Synthesis of Organoboron Compounds

“…Additionally, organoboron species have been used as bio-isosteres [30][31] of carboxylic acids to alter the physicochemical properties of lead candidates in drug discovery. Furthermore, they are used as the versatile building blocks in organic synthesis for molecular transformations, [32][33][34][35] and act as essential reaction partners in Suzuki-Miyaura cross-coupling reactions [36][37] or Chan-Lam reactions. [38] Over the last few years, there has been a growing interest in developing practical and convenient methods for the synthesis of organoboron compounds, either by traditional organic synthesis based on highly reactive organolithium or Grignard reagents with electrophilic boron species, followed by transesterification and hydrolysis [39][40][41][42][43] or photochemical catalysis.…”

Understanding the Mechanism and Selectivity of 1,1-Diborylalkanes from Alkenes Catalyzed by a Zirconium Complex

“…The 1,1-diborylalkanes as a significant class of organoboron compounds are versatile building blocks and very important intermediates in organic synthesis. − Several methods, including boronation reactions of halides, hydroboration of vinyl boronate esters (VBEs), dihydroboration of alkynes, insertion of diazoalkanes into diboron compounds, Ir- or Co-catalyzed benzylic C–H diboration, direct C–H boration of alkyl boronate esters, and deoxygenative diboration of carbonyl compounds have been used in developing 1,1-diborylalkanes. − However, they are less practical because of the limitations of their substrate scope. Therefore, as shown in Figure a, the strategy of synthesizing 1,1-diborylalkanes from readily available alkenes has been proposed, but it has not been widely reported.…”

Recent advances in the synthesis and reactivity of MIDA boronates

“…8 Also, a recently published review article on organoboron chemistry from Marder, Hall, Aggarwal, Morken, Fernández, Szabo, and others that do not cover this important topic. 9 In this review, we will summarize the different methods known to date for the synthesis and functionalization of MIDA-boronates in a chronological manner (Scheme 1).…”