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采用量子化学从头计算方法研究了噻唑烷并手性口恶唑硼烷催化剂催化芳香酮的不对称还原反应 .选用Hartree Fock方法 ,在STO 3g基组下对体系进行了全优化计算 .该催化剂具有扭曲的椅式构型 ,反应中首先在N原子处与硼烷配位生成催化剂 硼烷加合物 ,然后再与芳香酮形成具有 3种构型的催化剂 硼烷 芳香酮加合物 ,其中最有利于H转移并决定还原产物手性的构型具有次低的能量 .H转移后形成的催化剂 烷氧基硼烷加合物中含有一个稳定的B O B N四元环 .
The asymmetric reduction of aromatic ketone catalyzed by thiazolidine and chiral oxazaborolidine was studied by ab initio quantum chemistry method. The system was fully optimized using Hartree Fock method under the STO 3g basis. The catalyst has Twisted chair configuration, the reaction of the first in the N atom borane coordination with the catalyst borane adduct, and then with the aromatic ketone to form a catalyst with three configurations borane aromatic ketone adduct, the most The configuration favoring H transfer and determining the chirality of the reduced product has the second lowest energy.The catalyst alkoxyborane adduct formed after H transfer contains a stable BOBN quaternary ring.