Experiments indicate that a catalytic amount of Cul plays an important role in the siloxane-mediated Pd-catalyzed cross-coupling reactions with the direct use of organolithium reagents.Addition of organolithium to the...Experiments indicate that a catalytic amount of Cul plays an important role in the siloxane-mediated Pd-catalyzed cross-coupling reactions with the direct use of organolithium reagents.Addition of organolithium to the siloxane transfer agent generates an organosilicon intermediate.DFT calculations indicate that Cul initially accelerates the Si-Pd(Ⅱ) transmetalation of the organosilicon intermediate by the formation of CuI_(2)^(-).Subsequently,CuI_(2)^(-)works as a shuttle between the Si-Cu(Ⅰ) and Cu(Ⅰ)-Pd(Ⅱ)transmetalation processes.展开更多
基金financially supported by the National Natural Science Foundation of China(No.21803030)the Fundamental Research Funds for the Central Universities,the National Thousand Young Talents Program+3 种基金the Jiangsu Innovation&Entrepreneurship Talents Planthe NSF of Jiangsu Province(No.BK20170631)in Chinathe National Institutes of Health(No.CA-019033)the National Science Foundation in USA(No.CHE-1361104)。
文摘Experiments indicate that a catalytic amount of Cul plays an important role in the siloxane-mediated Pd-catalyzed cross-coupling reactions with the direct use of organolithium reagents.Addition of organolithium to the siloxane transfer agent generates an organosilicon intermediate.DFT calculations indicate that Cul initially accelerates the Si-Pd(Ⅱ) transmetalation of the organosilicon intermediate by the formation of CuI_(2)^(-).Subsequently,CuI_(2)^(-)works as a shuttle between the Si-Cu(Ⅰ) and Cu(Ⅰ)-Pd(Ⅱ)transmetalation processes.
