The cross-electrophile dialkylation of alkenes enables the formation of two C(sp)-C(sp) bonds from readily available starting materials in a single transformation, thereby providing a modular and expedient approach to building structural complexity in organic synthesis. Herein, we exploit the disparate electronic and steric properties of alkyl halides with varying degrees of substitution to accomplish their selective activation and addition to alkenes under electrochemical conditions. This method enables regioselective dialkylation of alkenes without the use of a transition-metal catalyst and provides access to a diverse range of synthetically useful compounds.
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http://dx.doi.org/10.1021/jacs.3c06794 | DOI Listing |
Chem Commun (Camb)
December 2024
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, 325035, P. R. China.
A selective green-light-induced hydroselenation of alkenes with diselenides using Hantzsch ester as the hydrogen donor has been developed. In the case of electron-neutral diaryl diselenides and diacyl ones, alkenes undergo anti-Markovnikov-selective hydroselenation. When switching to electron-deficient diaryl diselenides and dialkyl ones, Markovnikov-selective hydroselenation occurs.
View Article and Find Full Text PDFAdv Sci (Weinh)
December 2024
Guangming Advanced Research Institute, Department of Chemistry, and Guangdong Provincial Key Laboratory of Catalysis Southern University of Science and Technology, Shenzhen Grubbs Institute, Shenzhen, Guangdong, 518055, P. R. China.
Enantioenriched unsymmetric dialkyl carbinol derivatives are of importance in natural products, bioactive molecules, and functional organic materials. However, the catalytic asymmetric synthesis of dialkyl carbinol derivatives remains challenging due to the similar steric and electronic properties of two alkyl substituents. Herein, an unprecedented synthesis of chiral dialkyl carbinol ester derivatives from Ni-catalyzed reductive-oxidative relay cross-coupling of two alkenes is developed for the first time.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Laboratoire de Chimie des Polymères Organiques (LCPO), Université de Bordeaux, CNRS, Bordeaux INP, UMR 5629, 16 av. Pey Berland, 33607, Pessac cedex, France.
The quest for polymers that would be at the same time bio-based and degradable after usage, in addition to offering chemical post-modification options, remains a daunting challenge in contemporary polymer science. Despite advances in polymer chemistry, attempts at controlling the chain-growth polymerization of muconate esters remain unexplored. Here we show that dialkyl muconates can be rapidly polymerized by organocatalyzed group transfer polymerization (O-GTP).
View Article and Find Full Text PDFJ Am Chem Soc
August 2024
Department of Chemistry, Research Center for Molecular Recognition and Synthesis, Fudan University, Shanghai 200433, China.
Electrophilic addition of alkenes is a textbook reaction that plays a pivotal role in organic chemistry. In the past decades, catalytic asymmetric variants of this important type of reaction have witnessed great achievements by the development of novel catalytic systems. However, enantioselective aza-electrophilic additions of unactivated alkenes, which could provide a transformative strategy for the preparation of synthetically significant nitrogen-containing compounds, still remain a formidable challenge.
View Article and Find Full Text PDFJ Am Chem Soc
July 2024
Department of Chemistry, Duke University, Durham, North Carolina 27708, United States.
We introduce a method for the ()-selective aminoallylation of a range of ketones to prepare allylic 1,2-amino tertiary alcohols with excellent diastereo- and enantioselectivity. Copper-catalyzed reductive couplings of 2-azatrienes with aryl/alkyl and dialkyl ketones proceed with Ph-BPE as the supporting ligand, generating -amino alcohols with >98% ()-selectivity under mild conditions. The utility of the products is highlighted through several transformations, including those that leverage the ()-allylic amine moiety for diastereoselective reactions of the alkene.
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