C-2-Symmetric Hindered "Sandwich" Chiral N-Heterocyclic Carbene Precursors and Their Transition Metal Complexes: Expedient Syntheses, Structural Authentication, and Catalytic Properties | |
Shen, Hong-Qiang; Liu, Cong; Zhou, Yong-Gui; Chen, Mu-Wang | |
刊名 | ORGANOMETALLICS |
2018-11-12 | |
卷号 | 37期号:21页码:3756-3769 |
ISSN号 | 0276-7333 |
DOI | 10.1021/acs.organomet.8b00492 |
通讯作者 | Zhou, Yong-Gui(ygzhou@dicp.ac.cn) |
英文摘要 | We present here a new family of C-2-symmetric "sandwich" NHC ligands abbreviated as SITLAr and BzITL(Ar) and their complexes. The chiral fragments incorporate bulky yet flexible cyclohexyl groups with alpha-stereocenters joined to nitrogens individually, which set up chiral pockets around pivotal carbene carbons (less than 2.5 angstrom). Full characterization revealed unique structures with roughly parallel aryl moieties above and below imidazoline and benzimidazole planes in the Z-shaped arrangement. Extra hydrogen bonding interactions and steric stress between the square-planar frameworks and aryl groups led to the exceptional confinement and reversed the configurations in the iridium complexes. In accordance with Tolman's electronic parameters and topographic steric maps of well-established metalated complexes, these new ligands possess strong electron-donating properties and exceptionally steric demands. Additionally, the preliminary results employing the BzITL(Ar) ligands allowed appropriate activities and provided potential applications for asymmetric induction in the enantioselective aryl transfer and hydrosilylation reactions with moderate enantioselectivity. |
资助项目 | National Natural Science Foundation of China[21690074] ; National Natural Science Foundation of China[21532006] ; Dalian Bureau of Science and Technology[2016RD07] ; China Postdoctoral Science Foundation[2015M581366] |
WOS关键词 | ALLYLIC ALKYLATION ; ARYLBORONIC ACIDS ; RESTRICTED FLEXIBILITY ; NUCLEOPHILIC CARBENES ; ASYMMETRIC ADDITION ; IMIDAZOLIUM SALTS ; STERIC PROPERTIES ; NHC COMPLEXES ; LIGANDS ; EFFICIENT |
WOS研究方向 | Chemistry |
语种 | 英语 |
出版者 | AMER CHEMICAL SOC |
WOS记录号 | WOS:000450374500015 |
资助机构 | National Natural Science Foundation of China ; National Natural Science Foundation of China ; Dalian Bureau of Science and Technology ; Dalian Bureau of Science and Technology ; China Postdoctoral Science Foundation ; China Postdoctoral Science Foundation ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Dalian Bureau of Science and Technology ; Dalian Bureau of Science and Technology ; China Postdoctoral Science Foundation ; China Postdoctoral Science Foundation ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Dalian Bureau of Science and Technology ; Dalian Bureau of Science and Technology ; China Postdoctoral Science Foundation ; China Postdoctoral Science Foundation ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Dalian Bureau of Science and Technology ; Dalian Bureau of Science and Technology ; China Postdoctoral Science Foundation ; China Postdoctoral Science Foundation |
内容类型 | 期刊论文 |
源URL | [http://cas-ir.dicp.ac.cn/handle/321008/166556] |
专题 | 大连化学物理研究所_中国科学院大连化学物理研究所 |
通讯作者 | Zhou, Yong-Gui |
作者单位 | Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Peoples R China |
推荐引用方式 GB/T 7714 | Shen, Hong-Qiang,Liu, Cong,Zhou, Yong-Gui,et al. C-2-Symmetric Hindered "Sandwich" Chiral N-Heterocyclic Carbene Precursors and Their Transition Metal Complexes: Expedient Syntheses, Structural Authentication, and Catalytic Properties[J]. ORGANOMETALLICS,2018,37(21):3756-3769. |
APA | Shen, Hong-Qiang,Liu, Cong,Zhou, Yong-Gui,&Chen, Mu-Wang.(2018).C-2-Symmetric Hindered "Sandwich" Chiral N-Heterocyclic Carbene Precursors and Their Transition Metal Complexes: Expedient Syntheses, Structural Authentication, and Catalytic Properties.ORGANOMETALLICS,37(21),3756-3769. |
MLA | Shen, Hong-Qiang,et al."C-2-Symmetric Hindered "Sandwich" Chiral N-Heterocyclic Carbene Precursors and Their Transition Metal Complexes: Expedient Syntheses, Structural Authentication, and Catalytic Properties".ORGANOMETALLICS 37.21(2018):3756-3769. |
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