Enantioselective Rhodium-Catalyzed Cycloisomerization of 1,6-Allenynes to access 5/6-Fused Bicycle[4.3.0] nonadienes

Deng, Xu1,2,3,4,5; Shi, Li-Yang4,5; Lan, Jialing1,2,6; Guan, Yu-Qing4,5; Zhang, Xiaoyong1,2; Lv, Hui4,5; Chung, Lung Wa1,2; Zhang, Xumu1,2

2019-02-27

10.1038/s41467-019-08900-z

Nature Communications   影响因子和分区

2041-1723

Transition-metal-catalyzed cycloisomerization of 1,n-allenynes represents a powerful synthetic tool to rapidly assemble complex polycyclic skeletons from simple linear substrates. Nevertheless, there are no reports of the asymmetric version of these reactions. Moreover, most of these reactions proceed through a 6-endo-dig cyclization pathway, which preferentially delivers the distal product (via 5/5 rhodacyclic intermediate) rather than the proximal one (via 6/5 rhodacyclic intermediate). Herein, we report an enantioselective rhodium(I)-catalyzed cycloisomerization of 1,6-allenynes to provide the proximal product 5/6-fused bicycle[4.3.0]nonadienes in good yields and with excellent enantioselectivities. Remarkably, this chemistry works perfectly for 1,6-allenynes having a cyclic substituent within the allene component, thereby affording synthetically formidable tricyclic products with excellent enantioselectivities. Moreover, extensive DFT calculations suggest an uncommon pathway involving 5-exo-dig cycloisomerization, ring-expansion, rate-determining alkene isomerization involving C-sp3-H activation, C-C activation of the cyclobutene moiety and finally reductive elimination. Deuterium labeling experiments support the rate-determining step involving the C-H bond activation in this transformation.

SCI

英语

NI论文

第一 ; 通讯

Changsha Science and Technology Projects[kq1701088]

Science & Technology - Other Topics

Multidisciplinary Sciences

WOS:000459802500003

NATURE PUBLISHING GROUP

Web of Science

1.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518055, Peoples R China
2.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
3.Cent S Univ, Coll Xiangya Pharmaceut Sci, Changsha 410013, Hunan, Peoples R China
4.Wuhan Univ, Key Lab Biomed Polymers, Minist Educ, Wuhan 430072, Hubei, Peoples R China
5.Wuhan Univ, Engn Res Ctr Organosilicon Cpds & Mat, Minist Educ, Coll Chem & Mol Sci, Wuhan 430072, Hubei, Peoples R China
6.Harbin Inst Technol, Sch Chem & Chem Engn, Harbin 150001, Heilongjiang, Peoples R China

Deng, Xu,Shi, Li-Yang,Lan, Jialing,et al. Enantioselective Rhodium-Catalyzed Cycloisomerization of 1,6-Allenynes to access 5/6-Fused Bicycle[4.3.0] nonadienes[J]. Nature Communications,2019,10.

Deng, Xu.,Shi, Li-Yang.,Lan, Jialing.,Guan, Yu-Qing.,Zhang, Xiaoyong.,...&Zhang, Xumu.(2019).Enantioselective Rhodium-Catalyzed Cycloisomerization of 1,6-Allenynes to access 5/6-Fused Bicycle[4.3.0] nonadienes.Nature Communications,10.

Deng, Xu,et al."Enantioselective Rhodium-Catalyzed Cycloisomerization of 1,6-Allenynes to access 5/6-Fused Bicycle[4.3.0] nonadienes".Nature Communications 10(2019).