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.
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