TY - JOUR
T1 - Gold-catalyzed cycloisomerization of 1,6-diyne carbonates and esters to 2,4a-dihydro-1 H-fluorenes
AU - Rao, Weidong
AU - Koh, Ming Joo
AU - Li, Dan
AU - Hirao, Hajime
AU - Chan, Philip Wai Hong
PY - 2013/5/29
Y1 - 2013/5/29
N2 - A synthetic method to prepare 2,4a-dihydro-1H-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 n-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 American Chemical Society.
AB - A synthetic method to prepare 2,4a-dihydro-1H-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 n-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 American Chemical Society.
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U2 - 10.1021/ja4032727
DO - 10.1021/ja4032727
M3 - RGC 21 - Publication in refereed journal
SN - 0002-7863
VL - 135
SP - 7926
EP - 7932
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 21
ER -