Recent Advances in Metal-Catalyzed Alkyl–Boron (C(sp3)–C(sp2)) Suzuki-Miyaura Cross-Couplings

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.

Impact of Cross-Coupling Reactions in Drug Discovery and Development

“…The development of synthetic methodology has evolved [ 21 ] to meet the need for preparing 3D-type molecules, including rhodium-catalyzed asymmetric Suzuki–Miyaura reaction with aryls, vinyls, heteroaryls, and heterocycles. Application of the asymmetric sp 2 -sp 3 Suzuki–Miyaura methodology [ 22 ] enabled the synthesis of clinical candidates preclamol ( 15 , a dopamine D2 receptor partial agonist studied for the treatment of schizophrenia), niraparib ( 16 , MK−4827, a 2017 approved poly-(ADP ribose) polymerase (PARP) inhibitor indicated for ovarian cancer), and natural product isoanabasine ( 17 ), which are all presented in Figure 3 with their corresponding Fsp 3 values calculated using SwissADME [ 23 ] online tool.…”

Photocatalytic Degradation of Ethiofencarb by a Visible Light-Driven SnIn4S8 Photocatalyst

“…The loading of the catalyst is a key parameter in catalytic applications [ 38 , 39 ]. First, blank adsorption experiments at different pH values in the dark (without exposure to visible light) revealed that the change of initial ethiofencarb concentrations after 12 h of mixing with SnIn 4 S 8 was less than 6% ( Supplementary Materials Figure S1 ).…”

Facile Synthesis of NH-Free 5-(Hetero)Aryl-Pyrrole-2-Carboxylates by Catalytic C–H Borylation and Suzuki Coupling

“…With the advent of transition metal-catalyzed reactions [ 40 , 41 , 42 , 43 , 44 ], derivatization of preformed pyrrole ring has grown as an alternate strategy for the synthesis of arylated pyrroles. However, preparation of pyrrole-based organometallic reagents employing halogen-metal exchange requires Boc-protection of the acidic N-H proton ( Figure 2 ) [ 45 ].…”