[reaction: see text] A variety of gamma,delta-unsaturated carbene complexes that feature a stereogenic center at the beta-carbon couple with 2-ethynylbenzaldehyde to afford hydrophenanthrene derivatives with a high degree of stereoinduction. The direction of stereoinduction is opposite for examples where the stereogenic center is acyclic vs examples where it is within a ring.
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http://dx.doi.org/10.1021/ol025808y | DOI Listing |
Angew Chem Int Ed Engl
May 2024
Department of Chemistry, Purdue University, West Lafayette, IN 47907, USA.
Stereoselective hydrogenation of tetrasubstituted olefins is an attractive method to access compounds with two contiguous stereocenters. However, homogeneous catalysts for enantio- and diastereoselective hydrogenation exhibit low reactivity toward tetrasubstituted olefins due to steric crowding between the ligand scaffold and the substrate. Monometallic heterogeneous catalysts, on the other hand, provide accessible surface active sites for hindered olefins but exhibit unpredictable and inconsistent stereoinduction.
View Article and Find Full Text PDFChemistry
April 2024
Institute of Organic Chemistry, Research Centre for Natural Sciences, H-1117, Budapest, Magyar tudósok körútja 2.
Utilization of chiral frustrated Lewis pairs as catalysts in enantioselective hydrogenation of unsaturated molecules represents a promising approach in asymmetric synthesis. In our effort to improve our current understanding of the factors governing the stereoselectivity in these catalytic processes, herein we examined the mechanism of direct hydrogenation of aromatic enamines catalyzed by a binaphthyl-based chiral amino-borane. Our computational analysis reveals that only one particular conformer of the key borohydride reaction intermediate can be regarded as a reactive form of this species.
View Article and Find Full Text PDFACS Catal
December 2023
Institut Für Organische Chemie, Universität Regensburg, Universitätstrasse 31, 93053 Regensburg, Germany.
An adaptable, sulfur-accelerated photoaerobic selenium-π-acid ternary catalyst system for the enantioselective allylic redox functionalization of simple, nondirecting alkenes is reported. In contrast to related photoredox catalytic methods, which largely depend on olefinic substrates with heteroatomic directing groups to unfold high degrees of stereoinduction, the current protocol relies on chiral, spirocyclic selenium-π-acids that covalently bind to the alkene moiety. The performance of this ternary catalytic method is demonstrated in the asymmetric, photoaerobic lactonization and cycloamination of enoic acids and unsaturated sulfonamides, respectively, leading to an averaged enantiomeric ratio (er) of 92:8.
View Article and Find Full Text PDFNature
January 2024
State Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, China.
Enzymes are recognized as exceptional catalysts for achieving high stereoselectivities, but their ability to control the reactivity and stereoinduction of free radicals lags behind that of chemical catalysts. Thiamine diphosphate (ThDP)-dependent enzymes are well-characterized systems that inspired the development of N-heterocyclic carbenes (NHCs) but have not yet been proved viable in asymmetric radical transformations. There is a lack of a biocompatible and general radical-generation mechanism, as nature prefers to avoid radicals that may be harmful to biological systems.
View Article and Find Full Text PDFNat Commun
November 2023
The Scripps Research Institute (TSRI), 10550 North Torrey Pines Road, La Jolla, CA, 92037, USA.
A wide range of Cu(II)-catalyzed C-H activation reactions have been realized since 2006, however, whether a C-H metalation mechanism similar to Pd(II)-catalyzed C-H activation reaction is operating remains an open question. To address this question and ultimately develop ligand accelerated Cu(II)-catalyzed C-H activation reactions, realizing the enantioselective version and investigating the mechanism is critically important. With a modified chiral BINOL ligand, we report the first example of Cu-mediated enantioselective C-H activation reaction for the construction of planar chiral ferrocenes with high yields and stereoinduction.
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