Synthesis of functionalized γ-lactone via Sakurai exo-cyclization/rearrangement of 3,3-bis(silyl) enol ester with a tethered acetal.
An efficient synthesis of functionalized γ-lactones has been developed involving Sakurai exo-cyclization/rearrangement of 3,3-bis(silyl) enol esters with a tethered acetal. While the steric and electronic effects of geminal bis(silane) favor the desired Sakurai pathway, the methoxy species formed in the deprotection step also facilitates both cyclization and rearrangement. The synthetic value of this approach has been demonstrated by efficiently transforming the E-vinylsilane into enyne and the γ-lactone moiety into multisubstituted THF.
†Key Laboratory of Drug-Targeting of Education Ministry and Department of Medicinal Chemistry, West China School of Pharmacy, Sichuan University, Chengdu 610041, P. R. China.
Zhiping
Z
Yin
†Key Laboratory of Drug-Targeting of Education Ministry and Department of Medicinal Chemistry, West China School of Pharmacy, Sichuan University, Chengdu 610041, P. R. China.
Zengjin
Z
Liu
†Key Laboratory of Drug-Targeting of Education Ministry and Department of Medicinal Chemistry, West China School of Pharmacy, Sichuan University, Chengdu 610041, P. R. China.
Zhenggang
Z
Huang
†Key Laboratory of Drug-Targeting of Education Ministry and Department of Medicinal Chemistry, West China School of Pharmacy, Sichuan University, Chengdu 610041, P. R. China.
Yang
Y
Chu
†Key Laboratory of Drug-Targeting of Education Ministry and Department of Medicinal Chemistry, West China School of Pharmacy, Sichuan University, Chengdu 610041, P. R. China.
Zhiwen
Z
Chu
†Key Laboratory of Drug-Targeting of Education Ministry and Department of Medicinal Chemistry, West China School of Pharmacy, Sichuan University, Chengdu 610041, P. R. China.
Jia
J
Hu
†Key Laboratory of Drug-Targeting of Education Ministry and Department of Medicinal Chemistry, West China School of Pharmacy, Sichuan University, Chengdu 610041, P. R. China.
Lu
L
Gao
†Key Laboratory of Drug-Targeting of Education Ministry and Department of Medicinal Chemistry, West China School of Pharmacy, Sichuan University, Chengdu 610041, P. R. China.|‡State Key Laboratory of Biotherapy, West China Hospital, Sichuan University, Chengdu 610041, P. R. China.
Zhenlei
Z
Song
D000080:Acetals / Q000737:chemistry*; D020650:Combinatorial Chemistry Techniques; D003500:Cyclization; D004952:Esters; D005663:Furans / Q000737:chemistry*; D007659:Ketones / Q000138:chemical synthesis; D007783:Lactones / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D012821:Silanes / Q000737:chemistry*; D013237:Stereoisomerism; D014753:Vinyl Compounds / Q000737:chemistry*
D000080:Acetals; D004952:Esters; D005663:Furans; D007659:Ketones; D007783:Lactones; D012821:Silanes; D014753:Vinyl Compounds; C476909:vinylsilane; C018674:tetrahydrofuran