Desymmetrization of meso-bisphosphates via rhodium catalyzed asymmetric allylic arylation

TETRAHEDRON

卷:75

Article

Jacques, Reece¹  Hell, Alexander M. L.¹  Pullin, Robert D. C.²  Fletcher, Stephen P.¹ 

[1] Univ Oxford, Chem Res Lab, Dept Chem, 12 Mansfield Rd, Oxford OX1 3TA, England

[2] Vertex Pharmaceut Europe Ltd, 86-88 Jubilee Ave,Milton Pk, Abingdon OX14 4RW, Oxon, England

关键词: Desymmetrization;    meso-bisphosphates;    Boronic acids;    Rhodium;    Asymmetric catalysis;    Suzuki-Miyaura coupling;   

DOI  :  10.1016/j.tet.2019.130560

来源: Elsevier

【 摘 要 】

The desymmetrization of meso-compounds allows for the unmasking of previously installed stereogenic centers, and quaternary centers are of special interest as they are frequently challenging to form with control in synthesis. Here, we report the desymmetrization of highly functionalized cyclic meso-bisphosphates via Rhodium-catalyzed enantioselective allylic arylation. The highly enantioselective introduction of functionalized (hetero)aryl moieties to a prostereogenic quaternary center generates three continuous stereogenic centers. Typical (hetero)arylboronic acids are tolerated in synthetically useful yields and excellent enantioselectivity. (C) 2019 Elsevier Ltd. All rights reserved.

【 授权许可】

Free