Substituent effects on axial chirality in 1-aryl-3,4-dihydroisoquinolines: controlling the rate of bond rotation

TETRAHEDRON

卷:72

Article

Rosello, Josep Mas^1,2  Staniland, Samantha¹  Turner, Nicholas J.³  Clayden, Jonathan^1,2 

[1] Univ Manchester, Sch Chem, Oxford Rd, Manchester M13 9PL, Lancs, England

[2] Univ Bristol, Sch Chem, Cantocks Close, Bristol BS8 1TS, Avon, England

[3] Univ Manchester, Manchester Inst Biotechnol, Sch Chem, 131 Princess St, Manchester M1 7DN, Lancs, England

关键词: Atropisomers;    Axial chirality;    QUINAP;    Biaryls;    Dihydroisoquinolines;   

DOI  :  10.1016/j.tet.2016.01.037

来源: Elsevier

【 摘 要 】

A series of 1-aryl-3,4-dihydroisoquinolines (DHIQs) were synthesized and their barriers to bond rotation were determined by means of VT-NMR, dynamic HPLC or racemization studies. Although they all presented lower rotational stability than the related 1-arylisoquinolines (such as QUINAP), certain 1-arylDHIQ structures had a sufficiently high barrier to bond rotation to show axial chirality. These compounds included 1-(2-triflyl-1-naphthyl)-4,5-dihydroisoquinoline 4h and 1-(2-diphenylphosphanyl-1-naphthyl)-4,5-dihydroisoquinoline 4i. This discovery opens the door to the development of a new group of axially chiral N,P ligands for asymmetric synthesis and also potentially to new strategies for the synthesis of axially chiral 1-arylisoquinolines. (C) 2016 Elsevier Ltd. All rights reserved.

【 授权许可】

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