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Synthesis of an octahydro-1,1 '-binaphthyl thioether ligand and comparison with unhydrogenated binaphthyl analogues

Albrow, V., Biswas, K., Crane, A., Chaplin, N., Easun, Timothy, Gladiali, S., Lygo, B. and Woodward, S. 2003. Synthesis of an octahydro-1,1 '-binaphthyl thioether ligand and comparison with unhydrogenated binaphthyl analogues. Tetrahedron: Asymmetry 14 (18) , pp. 2813-2819. 10.1016/S0957-4166(03)00583-4

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Abstract

Acylation of octahydro-BINOL with Me2NC(S)Cl, in the presence of NaH, allows the formation of 2-(OH)-2′-(Me2NC(S)O)-1,1′-C10H20. Subsequent Newman–Kwart rearrangement (275°C, 12 min) proceeds cleanly with a small amount of racemisation (96–97% ee). The equivalent BINOL-derived species undergoes an identical rearrangement (but with higher racemisation, 79–80%) and appreciable amounts of a thiophene by-product are formed. Semi-empirical calculations (PM3) predict a higher racemisation barrier for the octahydro compound and suggest that the Newman–Kwart rearrangement could proceed via a concerted pathway. The H8-BINOL derived compound can be modified to 2-(OH)-2′-(SBun)-1,1′-C10H20 and the BINOL species to 2-(OH)-2′-(SBut)-1,1′-C10H12. The former promotes the 1,4-addition of AlMe3 to non-3-en-2-one in 57% ee the latter in 63% ee.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Publisher: Elsevier
ISSN: 0957-4166
Last Modified: 04 Jun 2017 07:58
URI: http://orca.cf.ac.uk/id/eprint/71034

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