Gold-Catalyzed Cycloisomerization of 1,6-Diyne Carbonates and Esters to 2,4a-Dihydro‑1<i>H</i>‑fluorenes
2013-05-29T00:00:00Z (GMT) by
A synthetic method to prepare 2,4a-dihydro-1<i>H</i>-fluorenes efficiently from gold(I)-catalyzed 1,2-acyloxy migration/cyclopropenation/Nazarov cyclization of 1,6-diyne carbonates and esters is described. The suggested reaction pathway provides rare examples of [2,3]-sigmatropic rearrangement in this class of compounds as well as the involvement of an in situ formed cyclopropene intermediate in gold catalysis. Experimental and ONIOM(QM:QM′) [our own <i>n</i>-layered integrated molecular orbital and molecular mechanics(quantum mechanics:quantum mechanics′)] computational studies based on the proposed Au carbenoid species provide insight into this unique selectivity.
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