TY - JOUR
T1 - Regioselectivity in α-Cleavage Reactions
T2 - Arylalkylcyclopropenethiones
AU - Singh, Sharat
AU - Ramamurthy, Vaidyanathan
PY - 1985/10
Y1 - 1985/10
N2 - Photoreactions of several arylalkylcyclopropenethiones (1b-e) have been investigated. The products formed have been rationalized on the basis of α-cleavage as the primary photoprocess. The photochemical α-cleavage is presumed to originate from the lowest excited nπ* triplet state. A regioselective α-cleavage reaction has been observed and this unusual regioselectivity is explained on the basis of close approach of the ground-state energy surface of the diradical/carbene, the primary intermediates, to the excited triplet-state surface of cyclopropenethiones. Reactions originating from both triplet and singlet thioketene carbene have been observed upon photolysis of arylalkylcyclopropenethiones.
AB - Photoreactions of several arylalkylcyclopropenethiones (1b-e) have been investigated. The products formed have been rationalized on the basis of α-cleavage as the primary photoprocess. The photochemical α-cleavage is presumed to originate from the lowest excited nπ* triplet state. A regioselective α-cleavage reaction has been observed and this unusual regioselectivity is explained on the basis of close approach of the ground-state energy surface of the diradical/carbene, the primary intermediates, to the excited triplet-state surface of cyclopropenethiones. Reactions originating from both triplet and singlet thioketene carbene have been observed upon photolysis of arylalkylcyclopropenethiones.
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U2 - 10.1021/jo00220a012
DO - 10.1021/jo00220a012
M3 - Article
AN - SCOPUS:33748167851
VL - 50
SP - 3732
EP - 3738
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 20
ER -