Nickel-Catalyzed Desymmetric Hydrogenation of Cyclohexadienones: An Efficient Approach to All-Carbon Quaternary Stereocenters

You, Cai1; Li, Xiuxiu1; Gong, Quan1; Wen, Jialin1,2; Zhang, Xumu1,3

2019-09-18

10.1021/jacs.9b07957

Journal of the American Chemical Society   影响因子和分区

0002-7863

1520-5126

Nickel-catalyzed desymmetric hydrogenation has been achieved. With the Ni(OTf)(2)/(S,S)-Ph-BPE system, a series of gamma,gamma-disubstituted cyclohexadienones were transformed to the corresponding cyclohexenones with a chiral all-carbon quaternary center at the gamma position in high yields (92-98%) and excellent enantioselectivities (92%-99% ee). This catalytic system can also tolerate the desymmetric reaction of spirocarbocyclic cyclohexadienones to produce the corresponding cyclohexenones bearing a chiral spiro quaternary carbon with high yields (94%-98%) and ee values (96%-99% ee). Furthermore, this methodology provides an efficient and concise synthetic route to the intermediate of natural products cannabispirenones A and B.

SCI ; EI ; IC ; CCR

英语

NI期刊 ; NI论文

第一 ; 通讯

Shenzhen Commission of Science, Technology and Innovation[JSGG20160608140847864]

Chemistry

Chemistry, Multidisciplinary

WOS:000487180200018

AMER CHEMICAL SOC

20194107512611

Carbon ; Catalysis ; Hydrogenation ; Ketones ; Nickel

Nickel:548.1 ; Chemical Reactions:802.2 ; Chemical Products Generally:804 ; Organic Compounds:804.1

Web of Science

1.Southern Univ Sci & Technol, Dept Chem, 1088 Xueyuan Rd, Shenzhen 518055, Peoples R China
2.Southern Univ Sci & Technol, Acad Adv Interdisciplinary Studies, 1088 Xueyuan Rd, Shenzhen 518055, Peoples R China
3.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, 1088 Xueyuan Rd, Shenzhen 518055, Peoples R China

You, Cai,Li, Xiuxiu,Gong, Quan,et al. Nickel-Catalyzed Desymmetric Hydrogenation of Cyclohexadienones: An Efficient Approach to All-Carbon Quaternary Stereocenters[J]. Journal of the American Chemical Society,2019,141(37):14560-14564.

You, Cai,Li, Xiuxiu,Gong, Quan,Wen, Jialin,&Zhang, Xumu.(2019).Nickel-Catalyzed Desymmetric Hydrogenation of Cyclohexadienones: An Efficient Approach to All-Carbon Quaternary Stereocenters.Journal of the American Chemical Society,141(37),14560-14564.

You, Cai,et al."Nickel-Catalyzed Desymmetric Hydrogenation of Cyclohexadienones: An Efficient Approach to All-Carbon Quaternary Stereocenters".Journal of the American Chemical Society 141.37(2019):14560-14564.