Gold-Catalyzed Cycloisomerization of 1,6-Diyne Carbonates and Esters to 2,4a-Dihydro‑1<i>H</i>‑fluorenes Weidong Rao Ming Joo Koh Dan Li Hajime Hirao Philip Wai Hong Chan 10.1021/ja4032727.s003 https://acs.figshare.com/articles/dataset/Gold_Catalyzed_Cycloisomerization_of_1_6_Diyne_Carbonates_and_Esters_to_2_4a_Dihydro_1_i_H_i_fluorenes/2410978 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. 2013-05-29 00:00:00 ONIOM gold catalysis carbenoid species reaction pathway