1-Thiadecalin bonds

This transannular addition of a-sulfinyl carbanions to nonactivated double bonds is utilized as the key step in a synthesis of trans-1-thiadecalin (70) in enantiomerically pure form. The required ( )-thiacy-clodec-4-ene 5-oxide (66a,b) was prepared via several steps frtm (/ ,/ )-l,6-dibromo-3,4-hexanediol. Upon treatment with butyllithium, a 4 1 mixture of isomeric sulfoxides (66a and 66b) undergoes smooth cyclizadon to give a mixture of isomeric bicyclic sulfoxides (67a and 67b) in the same 4 1 ratio as the starting material, suggesting that the cyclizadon is essentially stereospecific. The major isomer (67a) is reduced with PCb to a sulfide (68) from which the desired (70) is derived via a thiaoctaline (69 heme 16). 

NCS in pyridine gave 2,6-diphenyldihydro-4H-thiopyran-4-one. Full details of the kinetically controlled additions of various photogenerated carbenes and nitrenes to 4-t-butylthian have been published. Only -aryl sulphimides with equatorial S—N bonds were obtained from conformationally mobile or rigid thians and from CIS- and rra s-l-thiadecalins. ... 

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