Theoretical study on the mechanism of iridium-catalyzed gamma-functionalization of primary alkyl C-H bonds
Li, Z; Xia MR(夏苗仁); Xia, MR; Boyd, RJ
刊名CANADIAN JOURNAL OF CHEMISTRY
2016
卷号94期号:12页码:1028-1037
关键词iridium catalysis reaction mechanism C-H functionalization DFT calculation regioselectivity
DOI10.1139/cjc-2016-0287
文章类型期刊论文
英文摘要The mechanism of the iridium-catalyzed functionalization of a primary C-H bond at the gamma position of an alcohol5 is investigated by density functional theory (DFT) calculations. A new Ir-III-Ir-V mechanism is found to be more feasible than the previously reported Ir-I-Ir-III mechanism. 10 In the Ir-III-Ir-V mechanism, the reaction begins with the initial formation of (Me(4)phen) Ir-III(H)[Si(OR) Et-2](2) from the catalyst precursor, [Ir(cod) OMe](2) (cod = 1,5-cyclooctadiene). The catalytic cycle includes five steps: (1) the insertion of norbornene into the Ir-H bond to produce (Me(4)phen) IrIII(norbornyl)[Si(OR) Et-2](2) (R = -CH(C2H5) C3H7); (2) the Si-H oxidative addition of HSi(OR) Et-2 to form (Me(4)phen) IrVH(norbornyl)[Si(OR) Et-2](3); (3) the reductive elimination of norbornane to furnish (Me(4)phen) IrIII[Si(OR) Et-2](3); (4) the intramolecular C-H activation of the primary C-H bond at the gamma position; and (5) the Si-C reductive elimination to produce the final product and regenerate the catalyst. The highest barrier in the IrIII-IrV mechanism is 7.3 kcal/mol lower than that of the Ir-I-Ir-III mechanism. In addition, the regioselectivity of the C-H activation predicted by this new Ir-III-Ir-V mechanism is consistent with experimental observation.
类目[WOS]Chemistry, Multidisciplinary
关键词[WOS]EFFECTIVE CORE POTENTIALS ; MOLECULAR CALCULATIONS ; BASIS-SETS ; ACTIVATION ; COMPLEXES ; BORYLATION ; DENSITY ; SILYLATION ; SILANES ; METHANE
语种英语
WOS记录号WOS:000390320300008
引用统计
文献类型期刊论文
条目标识符http://ir.ihep.ac.cn/handle/311005/260358
专题中国科学院高能物理研究所_多学科研究中心_期刊论文
作者单位中国科学院高能物理研究所
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Li, Z,Xia MR,Xia, MR,et al. Theoretical study on the mechanism of iridium-catalyzed gamma-functionalization of primary alkyl C-H bonds[J]. CANADIAN JOURNAL OF CHEMISTRY,2016,94(12):1028-1037.
APA Li, Z,夏苗仁,Xia, MR,&Boyd, RJ.(2016).Theoretical study on the mechanism of iridium-catalyzed gamma-functionalization of primary alkyl C-H bonds.CANADIAN JOURNAL OF CHEMISTRY,94(12),1028-1037.
MLA Li, Z,et al."Theoretical study on the mechanism of iridium-catalyzed gamma-functionalization of primary alkyl C-H bonds".CANADIAN JOURNAL OF CHEMISTRY 94.12(2016):1028-1037.
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