Theoretical study on the mechanism of iridium-catalyzed gamma-functionalization of primary alkyl C-H bonds

doi:10.1139/cjc-2016-0287

	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
DOI	10.1139/cjc-2016-0287
文献子类	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.
WOS关键词	EFFECTIVE CORE POTENTIALS ; MOLECULAR CALCULATIONS ; BASIS-SETS ; ACTIVATION ; COMPLEXES ; BORYLATION ; DENSITY ; SILYLATION ; SILANES ; METHANE
语种	英语
WOS记录号	WOS:000390320300008
内容类型	期刊论文
源URL	[http://ir.ihep.ac.cn/handle/311005/260358]
专题	中国科学院高能物理研究所
作者单位	中国科学院高能物理研究所
推荐引用方式 GB/T 7714	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.