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 ORCID: https://orcid.org/0000-0002-0713-2642, 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:	28 Oct 2022 08:30
URI:	https://orca.cardiff.ac.uk/id/eprint/71034

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