Ambivalent Role of Rotamers in Cyclic(alkyl)(amino)carbene Ruthenium Complexes for Enantioselective Ring-Opening Cross-Metathesis

被引：12

作者：

Morvan, Jennifer ^{[1
]}

Vermersch, Francois ^{[2
]}

Zhang, Ziyun ^{[3
]}

Vives, Thomas ^{[1
]}

Roisnel, Thierry ^{[1
]}

Crevisy, Christophe ^{[1
]}

Falivene, Laura ^{[4
]}

Cavallo, Luigi ^{[3
]}

Vanthuyne, Nicolas ^{[5
]}

Bertrand, Guy ^{[2
]}

Jazzar, Rodolphe ^{[2
]}

Mauduit, Marc ^{[1
]}

机构：

[1] Univ Rennes, Ecole Natl Super Chim Rennes, CNRS, ISCR UMR 6226, F-35000 Rennes, France

[2] Univ Calif San Diego, Dept Chem & Biochem, UCSD CNRS Joint Res Chem Lab UMI 3555, San Diego, CA 92093 USA

[3] King Abdullah Univ Sci & Technol KAUST, KAUST Catalysis Ctr KCC, Thuwal 239556900, Saudi Arabia

[4] Univ Salerno, Dipartimento Chim & Biol, I-84100 Fisiciano, SA, Italy

[5] Aix Marseille Univ, Cent Marseille, CNRS, iSm2, F-13013 Marseille, France

来源：

ORGANOMETALLICS | 2023年 / 42卷 / 06期

关键词：

CYCLIC (ALKYL)(AMINO)CARBENES CAACS; ASYMMETRIC OLEFIN METATHESIS; CATALYST ACTIVITY; CARBENES; BEARING; DESYMMETRIZATIONS; ENHANCEMENT; SELECTIVITY; REACTIVITY;

D O I：

10.1021/acs.organomet.3c00054

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The development of highly efficient enantioselective olefin metathesis catalysts is a significant challenge. Using optically pure chiral cyclic (alkyl)(amino)carbene (ChiCAAC) ligands combined with preliminary mechanistic insights and density functional theory (DFT) computations, we show that catalytic performances in this field can be impaired by the formation of rotamers before the enantio-determining step. Using DFT, we also demonstrate that these results can help accelerate the process of ligand discovery by providing faster methods to discriminate potential candidates.

引用

页码：495 / 504

页数：10

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