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