Pyranoside Phosphite-Oxazoline Ligands for the Highly Versatile and Enantioselective Ir-Catalyzed Hydrogenation of Minimally Functionalized Olefins. A Combined Theoretical and Experimental Study

被引：147

作者：

Mazuela, Javier ^{[2
]}

Norrby, Per-Ola ^{[1
]}

Andersson, Pher G. ^{[3
,4
]}

Pamies, Oscar ^{[2
]}

Dieguez, Montserrat ^{[2
]}

机构：

[1] Univ Gothenburg, Dept Chem, SE-41296 Gothenburg, Sweden

[2] Univ Rovira & Virgili, Dept Quim Fis & Inorgan, Tarragona 43007, Spain

[3] Uppsala Univ, Dept Biochem & Organ Chem, S-75123 Uppsala, Sweden

[4] Univ KwaZulu Natal, Sch Chem, Durban, South Africa

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2011年 / 133卷 / 34期

关键词：

ALLYLIC SUBSTITUTION-REACTIONS; ASYMMETRIC HYDROGENATION; TRISUBSTITUTED OLEFINS; MECHANISTIC INSIGHTS; IRIDIUM CATALYSTS; AMINO-ACIDS; D-GLUCOSE; COMPLEXES; HYDROFORMYLATION; CHEMISTRY;

D O I：

10.1021/ja204948k

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A modular set of phosphite-oxazoline (P,N) ligands has been applied to the title reaction. Excellent ligands have been identified for a range of substrates, including previously challenging terminally disubstituted olefins, where we now have reached enantioselectivities of 99% for a range of substrates. The selectivity is best for minimally functionalized substrates with at least a moderate size difference between geminal groups. A DFT study has allowed identification of the preferred pathway. Computational prediction of enantioselectivities gave very good accuracy.

引用

页码：13634 / 13645

页数：12

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