Computational study of the transmetalation process in the Suzuki–Miyaura cross-coupling of aryls

Pd-catalyzed Suzuki cross-Coupling reaction of bromostilbene: insights on the nature of the boron Species

“…11 Recently, theoretical studies strongly suggest that an organoborate [ArB(OH) 3 ] -is involved in the transmetalation step. [12][13][14] The fact that trihydroxyarylborates can be applied for the base-free Suzuki reaction with aryl halides is a strong experimental evidence. 8 Our results for the different boron species in the presence and absence of base (see Table 1) also goes in the same direction and our next step was to identify the boron species present during the coupling reaction.…”

A Quantum-Chemical DFT Approach to Elucidation of the Chirality Transfer Mechanism of the Enantioselective Suzuki–Miyaura Cross-Coupling Reaction

“…Critical structures are fully optimized using basis sets: 6-31G(d) for H, C, O, B, Br, and P, as well as LANL2DZ with one f function for Pd and without pseudopotential. Identical basis sets have been recently used for quantitative description of similar processes involving similar chemical molecules [21]. For elementary reaction, in which anionic species are involved, calculations using basis set with one diffusion function were performed in parallel to procedure described above.…”

“…The different possibilities of transmetallation reaction that may take place in the second stage of the asymmetric SM reaction were assessed. It has been shown that the transmetallation step in a typical SM coupling reaction does not proceed without the nucleophilic additive, which enhances the electron density at the boron atom through its coordination and formation of boron-ate adduct [20,21,24,65,66]. In an aqueous solution of inorganic bases, the role of this nucleophile may be played by the hydroxyl anion.…”

“…Since aryl-aryl bond forming cross-couplings are mechanistically quite similar, in our studies on enantioselective coupling we concentrated on the Suzuki-Miyaura reaction, which is usually applied as a method of first choice. The mechanics of the nonstereocontrolled Suzuki-Miyaura (and a few other couplings) reaction catalysed by complexes of nonchelating monophosphines has been studied in detail (Scheme 1) [20][21][22][23][24][25][26][27][28][29] and can be extrapolated to reactions catalysed by transition metal complexes of different types and to stereoselective transformations. At …”

Theoretical Study of Synthesis Mechanism and Electronic Structure for 3-Octylthien-2,5-ylenediethynylene-co-benzo[c]-1',2',5'- thiadiazo-3,6-ylenedi(2,5-thienylene)

“…其中有机聚合物太阳能电池 具有材料易得、材质轻、制备工艺简单而耗资低、可大 面积制成柔性膜等优点而成为人们关注的热点 [5] . 但是, 聚合物光伏太阳能电池的能量转换效率较低 [6] , [10,11] , [16,17] , 经过渡态 TS1…”