Three‐component allylic alkylation reaction of α‐diazo ketones with water and allyl carbonates for construction of homoallylic alcohols

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(17), P. 3616 - 3623

Published: June 20, 2024

Abstract A three‐component allylic alkylation reaction of α‐diazo ketones, water and allyl carbonate under the cooperative catalysis Rh 2 (OAc) 4 , Pd (dba) 3 Brønsted acid was disclosed. This method provides an expeditious access to α‐keto homoallylic alcohols in good high yields. Controlled experiments support that transformations proceed through cross‐interception two active intermediates Pd‐allyl species enol derived from oxonium ylides. Moreover, synthetic generated products enable creation motifs enriched with dense functional groups, underscoring their potential as valuable building blocks.

Language: Английский

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Nickel-Catalyzed Multicomponent Assembly of Alkynes toward α-CF₃-Alkenes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(26), P. 5566 - 5570

Published: June 21, 2024

We disclose an efficient nickel catalytic system for expediting the coupling of alkynes with fluoroalkyl hydrazones and boronic acids, thus facilitating synthesis stereospecific α-fluoroalkyl-alkene derivatives. 3H-Pyrazoles might be involved as key intermediates through a nitrogen-releasing process, enabling subsequent acids to afford 1,2-difunctional alkenes in highly step-economical fashion. This tandem platform demonstrates broad functional group tolerance, including complex natural products drug-like molecules.

Language: Английский

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Enantioselective Transfer Reactions of α-Heteroatom-Substituted Carbenes

Symmetry, Journal Year: 2024, Volume and Issue: 16(9), P. 1171 - 1171

Published: Sept. 6, 2024

Metal carbenes are widely acknowledged as a category of highly effective intermediates that facilitate otherwise inaccessible transformations. In recent decades, carbene chemistry has made considerable advances and demonstrated remarkable abilities in the formation diverse chemical bonds synthesis structurally distinctive molecules. Nevertheless, majority research within this field concentrated on α-carbon-substituted carbenes, with comparatively little investigation have been functionalized wider structural variety, particularly those substituted heteroatoms (e.g., O, N, P, S, Si, Ge, Sn B). The objective review is to elucidate advancements enantioselective transfer reactions involving metal these elements, thereby highlighting their contribution expansion diversity synthetic utility contemporary chemistry.

Language: Английский

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Asymmetric Multi-component Trifunctionalization Reactions with α-Halo Rh-Carbenes

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 16, 2024

Multi-component multi-functionalization reactions involving active intermediates are powerful tools for rapidly generating a wide array of compounds. Metal carbynoids, with their distinct reactivity, hold great promise developing new synthetic methodologies. However, application in catalytic transfer has been hindered by the limited availability suitable precursors. In this study, we investigate potential α-halo Rh-carbenes, leveraging concept metal carbynoids reactions. Through chiral phosphoric acid-catalyzed asymmetric trifunctionalization, have developed an innovative method synthesizing variety α-cyclic ketal β-amino esters high yields and excellent enantioselectivity. Our extensive experimental computational studies reveal that Rh-carbenes exhibit carbynoid properties, which facilitate transformation into functionalized Fischer-type through decomposition C-halo bond.

Language: Английский

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