Chen, XianxiaoZhou, YuanyuanJin, JianwenFarshadfar, KavehAriafard, AlirezaRao, WeidongChan, Philip Wai Hong2025-12-162025-12-161615-4150ORCID:/0000-0003-2383-6380/work/197987406https://hdl.handle.net/1885/733795595A synthetic method to prepare cycloalkyl- and (hetero)aryl-fused bicyclo[3.3.1]nonane derivatives from gold(I)-catalyzed cyclopropanation/[5+3] cycloaddition of 1,4,9- and 1,4,10-allenenynes is described. The suggested double cycloisomerization mechanism delineates the first example of a stepwise [5+3] cycloaddition pathway in gold catalysis, a mode of reactivity that is also sparse in organic chemistry. Experimental and Density Functional Theory (DFT) computational studies based on a proposed gold carbenoid species provides insight into this unique selectivity that leads to the assembly of the architecturally challenging bridged carbocyclic motif. (Figure presented.).This work was supported by National Natural Science Foundation of China (Grant No. 21502093), Project Funds from the National First-Class Disciplines (PNFD) and Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD) (to W.R.), and a Discovery Project Grant (DP160101682) from the Australian Research Council (to P.W.H.C).12en© 2019 The Author(s)carbocyclic synthesiscyclizationgoldhomogenous catalysissynthetic methods2020-03-0410.1002/adsc.20190126385078595754