69830-91-7Relevant articles and documents
Stereoselective synthesis of chiral δ-lactonesviaan engineered carbonyl reductase
Wang, Tao,Zhang, Xiao-Yan,Zheng, Yu-Cong,Bai, Yun-Peng
, p. 10584 - 10587 (2021/10/19)
A carbonyl reductase variant,SmCRM5, fromSerratia marcescenswas obtained through structure-guided directed evolution. The variant showed improved specific activity (U mg?1) towards most of the 16 tested substrates and gave high stereoselectivities of up to 99% in the asymmetric synthesis of 13 γ-/δ-lactones. In particular, SmCRM5showed a 13.8-fold higher specific activity towards the model substrate,i.e., 5-oxodecanoic acid, and gave (R)-δ-decalactone in 99% ee with a space-time yield (STY) of 301 g L?1d?1. The preparative synthesis of six δ-lactones in high yields and with high enantiopurities showed the feasibility of the biocatalytic synthesis of these high-value-added chemicals, providing a cost-effective and green alternative to noble-metal catalysis.
Diastereo- and Enantioselective Synthesis of (E)-δ-Boryl-Substituted anti-Homoallylic Alcohols in Two Steps from Terminal Alkynes
Miura, Tomoya,Oku, Naoki,Murakami, Masahiro
supporting information, p. 14620 - 14624 (2019/09/06)
We report the highly diastereo- and enantioselective preparation of (E)-δ-boryl-substituted anti-homoallylic alcohols in two steps from terminal alkynes. This method consists of a cobalt(II)-catalyzed 1,1-diboration reaction of terminal alkynes with B2pin2 and a palladium(I)-mediated asymmetric allylation reaction of the resulting 1,1-di(boryl)alk-1-enes with aldehydes in the presence of a chiral phosphoric acid. Propyne, which is produced as the byproduct during petroleum refining, could be used as the starting material to construct homoallylic alcohols that are otherwise difficult to synthesize with high stereocontrol.
Lewis Base/Br?nsted Acid Co-Catalyzed Asymmetric Thiolation of Alkenes with Acid-Controlled Divergent Regioselectivity
Luo, Hui-Yun,Dong, Jia-Wei,Xie, Yu-Yang,Song, Xu-Feng,Zhu, Deng,Ding, Tongmei,Liu, Yuanyuan,Chen, Zhi-Min
supporting information, p. 15411 - 15418 (2019/11/14)
A divergent strategy for the facile preparation of various enantioenriched phenylthio-substituted lactones was developed based on Lewis base/Br?nsted acid co-catalyzed thiolation of homoallylic acids. The acid-controlled regiodivergent cyclization (6-endo vs. 5-exo) and acid-mediated stereoselective rearrangement of phenylthio-substituted lactones were explored. Experimental and computational studies were performed to clarify the origins of the regioselectivity and enantioselectivity. The calculation results suggest that C?O and C?S bond formation might occur simultaneously, without formation of a commonly supposed catalyst-coordinated thiiranium ion intermediate and the potential π–π stacking between substrate and SPh as an important factor in the enantio-determining step. Finally, this methodology was applied in the rapid syntheses of the bioactive natural products (+)-ricciocarpin A and (R)-dodecan-4-olide.