Abstract
AbstractDirect and sensitized photolyses of 1‐biphenylyl‐2,2‐dimethylcyclopropane gave 2‐methyl‐4‐biphenylyl‐1‐butene as sole product. Comparison of the product formation quantum yields at zero conversion in direct and sensitized photolyses (1.7 × 10−3 vs. 1.8 × 10−3) indicated that the rearrangement took place from the triplet excited state in both cases. A stepwise mechanism involving disrotatory ring opening of the cyclopropane and subsequent 1,3‐H suprafacial shift is proposed and is consistent with the reaction multiplicity result, the orbital and state correlation diagram analyses as well as the prediction based on the Large K and Small K Concept.
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