Highly E-selective all-carbon tetrasubstituted alkenes with a C(sp(3))-F unit have been synthesized through a dehydroxyfluorination of Morita-Baylis-Hillman (MBH) adducts which can be readily prepared from α,β-unsaturated carbonyl compounds and α-keto esters. A variety of subsequent transformations afforded monofluoromethyl substituted heterocycles in high yields.
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Amide-Directed Highly Enantioselective Hydrogenation of Diverse Acyclic Multisubstituted Alkenes Under Mild Conditions.
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January 2025
Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, Beijing, 100084, China.
Enantioselective hydrogenation of tetrasubstituted alkenes to form 1,2-contiguous stereocenters is a particularly appealing but highly challenging transformation in asymmetric catalysis. Despite the notable progress achieved in enantioselective hydrogenation over the past decades, enantioselective hydrogenation of all-carbon tetrasubstituted alkenes containing multiple alkyl groups remains an unsolved challenge. Here, we report a rhodium-catalyzed highly diastereo- and enantioselective hydrogenation of diverse acyclic multisubstituted alkenes under mild conditions.
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Université de Caen Normandie, ENSICAEN, CNRS, LCMT, Normandie University, 6 Bd. du Maréchal Juin, Caen 14050, France.
The ring-opening reaction of fluorinated oxetanes by halides, including alkylidene oxetanes and spirocyclic oxetanes, was highly stereoselective and directed by the presence of a fluorine atom. This reaction allowed a stereoselective preparation of tetrasubstituted alkenes and substituted pyrrolidines containing all-carbon quaternary centers. Theoretical calculations were performed to shed light on experimentally observed regioselectivity in the opening of oxetane derivatives.
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Chem Commun (Camb)
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School of Chemistry and Chemical Engineering, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, China.
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State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University Nanjing 210023 China.
Article Synopsis
- The study focuses on selective activation of benzylic C(sp)-H bonds for creating complex organic compounds, highlighting the challenges associated with selecting among similar C-H bonds.
- A site- and stereoselective method is introduced using metallaphotoredox catalysis, allowing for the production of various tri- and tetrasubstituted olefins from complex substrates with multiple benzylic sites.
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Org Lett
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Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Innovative Drug Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331, People's Republic of China.
A visible-light-induced intramolecular diradical-mediated hydrogen atom transfer (DHAT) of primary, secondary, and tertiary C(sp)-H bonds and subsequent cyclization is described. This transformation is enabled by triplet energy transfer upon Lewis acid coordination to alkyl-substituted arylvinylpyridines and gives access to a variety of benzocyclobutenes (>40 examples, 32-96% yield). Notably, tri- and tetrasubstituted olefins with tertiary C(sp)-H bonds effectively delivered sterically hindered products with adjacent all-carbon quaternary centers.
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