Abstract
Boron chemistry has evolved to become one of the most diverse and applied fields in organic synthesis and catalysis. Various valuable reactions such as hydroborylations and Suzuki–Miyaura cross-couplings (SMCs) are now considered as indispensable methods in the synthetic toolbox of researchers in academia and industry. The development of novel sterically- and electronically-demanding C(sp3)–Boron reagents and their subsequent metal-catalyzed cross-couplings attracts strong attention and serves in turn to expedite the wheel of innovative applications of otherwise challenging organic adducts in different fields. This review describes the significant progress in the utilization of classical and novel C(sp3)–B reagents (9-BBN and 9-MeO-9-BBN, trifluoroboronates, alkylboranes, alkylboronic acids, MIDA, etc.) as coupling partners in challenging metal-catalyzed C(sp3)–C(sp2) cross-coupling reactions, such as B-alkyl SMCs after 2001.
Highlights
Boron is a peculiar metalloid with fascinating chemical complexity
The energy-related uses of boron compounds range from high-energy fuels for advanced aircrafts to boron–nitrogen–hydrogen compounds as hydrogen storage materials for fuel cells [2]
Suzuki–Miyaura cross-couplings (SMCs) are unhindered electron-rich organoboranes and electron-deficient coupling partners. This type of coupling is highly affected by all the reaction parameters including the type of organoborane, base, solvent and metal catalyst, and the nature of the halide partner. The effects of these parameters were detailed in the review by Danishefsky et al on B–alkyl SMC in 2001 [33]
Summary
Boron is a peculiar metalloid with fascinating chemical complexity. The unusual properties of boron stem from its three valence electrons, which can be torn away, favoring metallicity and making it electron-deficient, yet sufficiently localized and tightly bound to the nucleus, allowing the insulating states to emerge [1]. The. SMC the reaction generally the conjoining of an organic halide or pseudohalide in the presence of palladium (or other relevant metal/ligand) as a catalyst organoboron reagent and an organic halide or pseudohalide in the presence of palladium This type of coupling is highly affected by all the reaction parameters including the type of organoborane, base, solvent and metal catalyst, and the nature of the halide partner The effects of these parameters were detailed in the review by Danishefsky et al on B–alkyl SMC in 2001 [33]. As mentioned in the introduction, SMC is the conjoining of an organoboron reagent and an organic halide or pseudohalide in the presence of palladium (or other relevant metal) as a catalyst and a base for the activation of the boron compound (Scheme 1B) [5,6,7]. Two main analysis routes can be outlined as can be seen in Scheme 2: A) Boronate pathway: tetracoordinate nucleophilic boronate species III is generated in situ and substitutes the halide ligand of the Pd intermediate I issued from the oxidative addition, followed by the elimination
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