Total Synthesis of Mesembrine – The Construction of Quaternary Stereocenters by Gold‐Catalyzed Diyne Desymmetrization

Czekelius, Constantin

doi:10.1002/ijch.201700060

Cited by 10 publications

(2 citation statements)

References 75 publications

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“…In 1987, the first homogeneous gold-catalyzed addition of nucleophiles to alkynes was realized by the group of Utimoto using sodium tetrachloroaurate dihydrate. , One decade later, Teles et al and Tanaka et al demonstrated the possibility of activating alkynes using gold(I) complexes. From that point, the field of gold(I) catalysis started to gain momentum year after year and still today remains one of the most active areas of research in organometallic chemistry. , This comes as a consequence of the ability of gold(I) complexes to activate π bonds in a very selective manner. − Its potential, attributed partially to relativistic effects, is illustrated by the wide molecular complexity − that can be built through the gold(I)-catalyzed cycloisomerization of enynes (Scheme ). − …”

Section: Introductionmentioning

confidence: 99%

Gold-Catalyzed Synthesis of Small Rings

et al. 2020

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Three- and four-membered rings, widespread motifs in nature and medicinal chemistry, have fascinated chemists ever since their discovery. However, due to energetic considerations, small rings are often difficult to assemble. In this regard, homogeneous gold catalysis has emerged as a powerful tool to construct these highly strained carbocycles. This review aims to provide a comprehensive summary of all the major advances and discoveries made in the gold-catalyzed synthesis of cyclopropanes, cyclopropenes, cyclobutanes, cyclobutenes, and their corresponding heterocyclic or heterosubstituted analogs.

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Section: Introductionmentioning

confidence: 99%

Gold-Catalyzed Synthesis of Small Rings

et al. 2020

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“…For example, the groups of Nishibayashi, Carreira, and Song have reported elegant propargylation methods to access quaternary carbon stereocenters, respectively. Czekelius and co-workers have developed enantioselective synthesis of alkyne substituted quaternary stereocenter through desymmetrization of diynamides . We are aware of only one example that generates alkyne-substituted all-carbon quaternary stereocenter through metal-catalyzed alkynyl addition.…”

Section: Introductionmentioning

confidence: 99%

Construction of Acyclic Quaternary Carbon Stereocenters by Catalytic Asymmetric Hydroalkynylation of Unactivated Alkenes

Wang

2019

J. Am. Chem. Soc.

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Quaternary carbon stereocenters are common structural motifs in organic synthesis. The construction of these stereocenters in a catalytic and enantioselective manner remains a prominent synthetic challenge. In particular, methods for the synthesis of alkyne-substituted quaternary carbon stereocenters are very rare. Previous catalytic systems for hydroalkynylation of alkenes create tertiary stereocenters. We describe here an iridium catalyzed asymmetric hydroalkynylation of nonactivated trisubstituted alkene. The hydroalkynylation of β,γ-unsaturated amides occurs with high regio-and enantioselectivities to afford alkyne-substituted acyclic quaternary carbon stereocenters. Computational and experimental data suggest that the enantioselectivity is not only determined by the facial selectivity of the alkene but also by an alkene isomerization process. This strategy provides an efficient method to access alkyne-substituted acyclic quaternary carbon stereocenters with minimally functionalized starting materials.

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Enantioselective Desymmetrization of 1,3‐Dicarbonyl Compounds through Transition‐Metal‐Catalyzed Intramolecular Cyclization Reactions

Liang,

Xie,

Cai

et al. 2024

ChemCatChem

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The development of reliable approaches to construct enantioenriched cyclic ketones bearing multiple stereocenters has attracted intense interest in synthetic chemistry, yet remains a challenging research area due to the difficulties in efficiently controlling the reaction enantioselectivity and diastereoselectivity. Desymmetrization of C2‐symmetric prochiral substrates has witnessed a practical and accessible strategy for creating more than one stereocenters in a single operation. In recent years, enantioselective desymmetrization of 1,3‐dicarbonyl compounds has been developed via transition‐metal‐catalyzed transformations for facile assembly of optically active cyclic ketones bearing congested stereocenters with diverse functionality. In this review, we would like to describe intramolecular enantioselective desymmetrization reactions of 1,3‐dicarbonyl derivatives, including C2‐functional group tethered 1,3‐diketones and 1,3‐diesters. This review is organized according to types of tethered groups, which aims to highlight the recent advances and briefly discuss about future perspectives in this domain.

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Total Synthesis of Mesembrine – The Construction of Quaternary Stereocenters by Gold‐Catalyzed Diyne Desymmetrization

Cited by 10 publications

References 75 publications

Gold-Catalyzed Synthesis of Small Rings

Gold-Catalyzed Synthesis of Small Rings

Construction of Acyclic Quaternary Carbon Stereocenters by Catalytic Asymmetric Hydroalkynylation of Unactivated Alkenes

Enantioselective Desymmetrization of 1,3‐Dicarbonyl Compounds through Transition‐Metal‐Catalyzed Intramolecular Cyclization Reactions

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