91083-82-8Relevant articles and documents
Photo-induced energy transfer relay of N-heterocyclic carbene catalysis: an asymmetric α-fluorination/isomerization cascade
Jiang, Xinhang,Li, En,Chen, Jiean,Huang, Yong
supporting information, p. 729 - 732 (2021/02/05)
The geometric configuration of olefin products is often driven by thermodynamic control in synthesis. Methods enabling switching of cis/trans selectivity are rare. Recently, photosensitized approaches have emerged as a powerful tool for accomplishing this task. In this report, we report an in situ isomerization of an N-heterocyclic carbene (NHC)-bound intermediate by a photo-induced energy transfer process that leads to selective access of chiral allylic fluorides with a cis-olefin geometry. In the absence of a photocatalyst or light, the reaction proceeds smoothly to give (E)-olefin products, while the (Z)-isomer can be obtained under photosensitizing conditions. Preliminary mechanistic experiments suggest that an energy transfer process might be operative. This journal is
Synthesis of Allylboranes via Cu(I)-Catalyzed B-H Insertion of Vinyldiazoacetates into Phosphine-Borane Adducts
Drikermann, Denis,M??el, Robert S.,Al-Jammal, Walid K.,Vilotijevic, Ivan
, p. 1091 - 1095 (2020/02/15)
Cu(I) catalysts enable C-B bond formation via direct insertion of vinyldiazoacetates into B-H bonds of borane-phosphine Lewis adducts to form phosphine-protected allylboranes under mild conditions. The resulting allylborane-phosphine Lewis adducts can be used in the diastereoselective allylation of aldehydes directly without the need for removal of the phosphine. The allylation reaction proceeds with high diastereoselectivity and yields 5,6-disubstituted dihydropyranones after treatment with an appropriate acid.
An Enzymatic Platform for the Highly Enantioselective and Stereodivergent Construction of Cyclopropyl-δ-lactones
Chandgude, Ajay L.,Fasan, Rudi,Liu, Ningyu,Ren, Xinkun
, p. 21634 - 21639 (2020/09/23)
Abiological enzymes offers new opportunities for sustainable chemistry. Herein, we report the development of biological catalysts derived from sperm whale myoglobin that exploit a carbene transfer mechanism for the asymmetric synthesis of cyclopropane-fused-δ-lactones, which are key structural motifs found in many biologically active natural products. While hemin, wild-type myoglobin, and other hemoproteins are unable to catalyze this reaction, the myoglobin scaffold could be remodeled by protein engineering to permit the intramolecular cyclopropanation of a broad spectrum of homoallylic diazoacetate substrates in high yields and with up to 99 % enantiomeric excess. Via an alternate evolutionary trajectory, a stereodivergent biocatalyst was also obtained for affording mirror-image forms of the desired bicyclic products. In combination with whole-cell transformations, the myoglobin-based biocatalyst was used for the asymmetric construction of a cyclopropyl-δ-lactone scaffold at a gram scale, which could be further elaborated to furnish a variety of enantiopure trisubstituted cyclopropanes.
