This review presents a comprehensive overview of transition-metal-catalyzed domino reactions of strained bicyclic alkenes, including both homo- and heterobicyclic alkenes. These compounds are important synthons in organic synthesis, providing an important platform for the construction of biologically/medicinally significant compounds which bear multiple stereocenters. The review has been divided according to the metal used in the reaction. An overview of the substrate scope, reaction conditions, and their potential applications in organic synthesis is discussed. A comprehensive outlook on the reactivity paradigms of homo- and heterobicyclic alkenes is discussed and should shed light on future directions for further development in this field.
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http://dx.doi.org/10.3762/bjoc.19.38 | DOI Listing |
Chemistry
July 2024
School of Natural Science, Department Chemie, Technische Universität München, Lichtenbergstr. 4, Garching bei München, 85748, Germany.
Syntheses of (partially) aromatic nitrogen heterocycles increasingly rely on transition-metal catalyzed C-C- and C-N-cross-coupling reactions. Here we describe a different approach to the synthesis of indolines by a domino C(sp)-H activation, 1,2-addition, and defluorinative SAr-cyclization sequence to provide the target 1,2-diarylindolines (1,2-diaryl-2,3-dihydroindoles) from ortho-fluorinated methyl-arenes and N-aryl imines (benzylidene anilines) in a cyclocondensation that is mediated by potassium hexamethyldisilazide (KHMDS) as base exclusively. This transition-metal-free process via C-H and C-F bond activation provides a one-step entry into a wide array of indoline scaffolds (43 examples, up to 96 % yield).
View Article and Find Full Text PDFJ Am Chem Soc
April 2024
Laboratory of Synthesis and Natural Products (LSPN), Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH5304, CH-1015 Lausanne, Switzerland.
Many elegant asymmetric syntheses of enantioenriched tertiary alcohols have been developed, and both the transition metal-catalyzed and the radical-based peripheral functionalization of tertiary alcohols have attracted intensive research interest in recent years. However, directly editing tetrasubstituted carbons remains challenging. Herein, we report a Pd-catalyzed migratory fluoroarylation reaction that converts tertiary alcohols to α-fluorinated tertiary alkyl ethers in good to excellent yields.
View Article and Find Full Text PDFBeilstein J Org Chem
April 2023
Guelph-Waterloo Centre for Graduate Work in Chemistry and Biochemistry, Department of Chemistry, University of Guelph, Guelph, Ontario, N1G 2W1, Canada.
This review presents a comprehensive overview of transition-metal-catalyzed domino reactions of strained bicyclic alkenes, including both homo- and heterobicyclic alkenes. These compounds are important synthons in organic synthesis, providing an important platform for the construction of biologically/medicinally significant compounds which bear multiple stereocenters. The review has been divided according to the metal used in the reaction.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
May 2023
Laboratory of Synthesis and Natural Products (LSPN), Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, 1015, Lausanne, Switzerland.
Transition-metal-catalyzed [4+2] heteroannulation of α,β-unsaturated oximes and their derivatives with alkynes has been developed into a powerful strategy for the synthesis of pyridines. It nevertheless lacks regioselectivity when unsymmetrically substituted alkynes are used. We report herein the unprecedented synthesis of polysubstituted pyridines by a formal [5+1] heteroannulation of two readily accessible building blocks.
View Article and Find Full Text PDFChem Soc Rev
January 2021
Organic Chemistry Department, University of Geneva, 30 quai Ernest Ansermet, Geneva 1211, Switzerland.
One-pot reactions elaborated around transition metal-catalyzed isomerization of alkenes not only offer the inherent advantages of atom-, step- and redox-economy but also enable the preparation of value-added products that would be difficult to access by conventional methods. In this Review, we cover seminal and recent examples of tandem, sequential and domino processes, which incorporate the most attractive features of olefin isomerization.
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