Direct β-C–H ketoalkylation of enaminoesters with cyclopropanols under metal-free conditions

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A TEMPO-mediated β-ketoalkylation of enaminoesters with cyclopropanols under metal-free conditions is herein described. This reaction provides a straightforward and highly efficient route to β-keto alkyl substituted for the first time, which could be rapidly efficiently converted into synthetically useful 2-alkoxycarbonyl functionalized 1,5-diketones. Moreover, practicability this protocol successfully demonstrated by scale-up experiments late-stage functionalization natural products pharmaceutically relevant molecules.

Language: Английский

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Ligand-controlled regiodivergent aminocarbonylation of cyclobutanols toward 1,1- and 1,2-substituted cyclobutanecarboxamides

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Oct. 31, 2024

Four-membered carbocycles are among the most sought-after backbones which commonly found in biologically active molecules. However, difficulties on their producing existing due to its highly strained ring system. On other hand, cyclobutanols can be straightforwardly prepared and serves as precursors for synthesizing cyclobutane derivatives. Here we report an example of regioselective aminocarbonylation core remained intact. The method exhibits good functional group compatibility, well high regio- stereoselectivity, offering new pathways several pharmaceuticals. Furthermore, this strategy enables rapid installation a conformational restricted skeleton, greatly facilitating direct access valuable drug molecules that require restriction.

Language: Английский

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Catalytic Construction of C(sp3)‐Ge Bonds: Recent Advances and Future Perspectives

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(22), P. 4618 - 4633

Published: Oct. 16, 2024

Abstract Germanium (Ge), a congener of carbon, possesses unique properties that hold extensive potential for applications across multiple domains. Recent years have seen significant progress in the development carbon‐germanium bond formation strategies, particularly those more challenging C( sp 3 )−Ge bonds. This review systematically summarizes recent advances forming methodologies, with particular emphasis on (1) versatility transition‐metals, including iron, nickel, copper, rhodium and palladium, as catalysts broadening reaction scope controlling selectivity; (2) powerfulness organic photocatalysis achieving mild selective formation, (3) sustainability catalytic electrosynthesis facilitating chemical oxidant‐/reductant‐ free conversions. Additionally, examples (4) non‐catalytic strategies are also discussed. The representative scopes, well mechanistic proposals, these protocols highlighted. Through an overview current state research, this aims to offer insights into construction bonds, provide perspectives future research directions address challenges.

Language: Английский

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Ring-Opening α,β-Difunctionalization of Cyclopropanols with Azides Enables 4-Keto-Functionalized 1,2,3-Triazole Synthesis

Organic Letters, Journal Year: 2024, Volume and Issue: 26(44), P. 9553 - 9557

Published: Oct. 28, 2024

Selective C–C bond cleavage and transformation of organic small molecules to create products increased value are one the central goals in chemistry. In this study, we have developed a novel TEMPO-mediated ring-opening α,β-difunctionalization cyclopropyl alcohols with azides prepare structurally important 4-keto-1,2,3-triazoles under metal- additive-free conditions. This protocol not only provides straightforward efficient method for synthesis 4-keto-functionalized 1,2,3-triazoles pot but also accomplishes goal constructing α,β-double C–N bonds via ring opening first time. Additionally, application skeletons drugs natural Kv1.5 channel blocker 4u further demonstrate synthetic potential practicability strategy.

Language: Английский

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Synthesis of ω-Chloroalkyl Aryl Ketones via C–C Bond Cleavage of tert-Cycloalkanols with Tetramethylammonium Hypochlorite

Molecules, Journal Year: 2024, Volume and Issue: 29(8), P. 1874 - 1874

Published: April 19, 2024

An oxidative C–C bond cleavage of tert-cycloalkanols with tetramethylammonium hypochlorite (TMAOCl) has been developed. TMAOCl is easy to prepare from hydroxide, and the combination AcOH effectively promoted in a two-phase system without additional phase-transfer reagents. Unstrained were transformed into ω-chloroalkyl aryl ketones moderate excellent yields under metal-free mild reaction conditions.

Language: Английский

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Synthesis of Functionalized Organosilicon Compounds/Distal Ketones via Ring-Opening Giese Addition of Cycloalkanols under Organophotocatalytic Conditions

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(10), P. 7187 - 7200

Published: April 26, 2024

Visible-light-induced organophotocatalyzed ring-opening followed by remote Giese addition of tertiary cycloalkanols with β-silylmethylene malonates has been developed under mild reaction conditions for the synthesis organosilicon compounds, bearing a ketone group distally substituted silyl an additional dialkyl malonate functional handle in moderate to good yields (34–72%). The protocol also worked well diverse Michael acceptors, such as alkylidene/benzylidene malonates, trifluoro methylidene malonate, benzylidene malononitrile, α-cyano-enone, and α-cyano vinyl sulfone, delivered desired valuable functionalized ketones. To showcase potential method, various synthetic transformations obtained product were demonstrated.

Language: Английский

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