Cesium and Phenoxide Interaction Enabled by Rh Overrides the Innate Solvent-Mediated Chemoselectivity DOI

Romin Gogoi,

Garima Jindal

ACS Catalysis, Год журнала: 2024, Номер 14(16), С. 12351 - 12358

Опубликована: Авг. 5, 2024

DLPNO-CCSD(T) calculations are carried out to understand the distinctive chemoselectivity in a Rh(II)-catalyzed carbene insertion into C(sp2)–H bond unprotected phenols without preinstalled directing groups. As per conventional rules of solvation and separated ion pair polar aprotic solvents like acetonitrile, reaction should have resulted an O–H insertion. However, our reveal transition state model that helps overriding innate acetonitrile. It involves explicit participation added Cs2CO3 base, where interaction between phenoxide oxygen Cs cation, but not as metal-bound phenoxide, is crucial for controlling chemoselectivity. Our study will be helpful developing further reactions with broad catalyst, substrate, solvent scope.

Язык: Английский

Mechanism and stereoselectivity in metal and enzyme catalyzed carbene insertion into X–H and C(sp2)–H bonds DOI
Reena Balhara, Ritwika Chatterjee, Garima Jindal

и другие.

Chemical Society Reviews, Год журнала: 2024, Номер 53(22), С. 11004 - 11044

Опубликована: Янв. 1, 2024

This review provides a mechanistic overview of asymmetric Fe, Cu, Pd, Rh, Au and heme-based enzymes catalyzed carbene insertion reactions to construct C–X (X = O, N, S, etc. ) C–C bonds, focusing on the stereochemical models.

Язык: Английский

Процитировано

4

A combined experimental and computational study reveals a crossover between conventional cross-coupling and carbene insertion pathways in a Pd catalyzed C(sp2)–H insertion DOI Creative Commons

Arushi Tyagi,

Kritika Gaur,

Anubhav Goswami

и другие.

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Computational (DFT and DLPNO-CCSD(T)) calculations along with experimental tools (deuterium labelling, kinetic studies using VTNA, ESI-HRMS UV) are used to probe the mechanism of a Pd(ii)-catalyzed enantioselective carbene insertion into C(sp2)-H indole. Using deuterium labelling studies, we demonstrate intermediacy metal-hydride species, which contrasts mechanistic routes for other transition metals (Rh, Fe, Au, Cu, etc.). Our VTNA study reveals order be one in both diazo indole, microkinetic modelling aligns well computationally predicted mechanism. The is further supported by detection most stable intermediate catalytic cycle ESI-HRMS. An investigation origin stereoselectivity DLPNO-CCSD(T) presents new paradigm, wherein stereocontrol arises during formation Pd itself as opposed proton transfer steps found all metal catalysts.

Язык: Английский

Процитировано

0

Calcium‐Catalyzed Multicomponent Reactions in Organic Synthesis DOI
Abhishek Pareek, Ravikrishna Dada, Srinivasarao Yaragorla

и другие.

Asian Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 19, 2025

Abstract Calcium catalysis has garnered significant attention from synthetic organic chemists as a sustainable alternative to Lewis acidic transition metals, rare‐earth and strong Brønsted acids. This alkaline earth metal, abundant in nature, environmentally benign, moisture‐tolerant, biodegradable, low toxicity, offers distinct advantages. catalysts exhibit exceptional proficiency activating diverse functional groups, particularly π‐activated species such ketones, alcohols, enamines, aldehydes, alkenes, alkynes, allenes, thereby enabling nucleophilic additions tandem chemical transformations. These characteristics resonate with the core tenets of green chemistry, enhancing atom step economy while minimizing waste generation. review presents thorough in‐depth analysis calcium‐catalyzed multi‐component reactions (MCRs), underscoring their transformative role advancing synthesis. Furthermore, it explores untapped potential calcium broadening horizons MCRs, fostering innovative eco‐friendly methodologies for applications pharmaceuticals materials science. Key challenges future prospects within this evolving domain are also critically examined.

Язык: Английский

Процитировано

0

Divergent Reactions of α-Diazo 1,3-Dicarbonyl Compounds with Allylic Carbonates Involving Ketene versus Carbene Intermediates Enabled by Cooperative Rh(II)/Pd(0) Dual Catalysis DOI

De-Xin Song,

Yuhua Song,

Heng-Hua Huang

и другие.

Organic Letters, Год журнала: 2024, Номер 26(37), С. 7920 - 7925

Опубликована: Сен. 9, 2024

A cooperative Rh(II)/Pd(0) dual-catalysis strategy that enabled divergent reactions of α-diazo 1,3-dicarbonyl compounds with allylic carbonates involving ketene versus carbene intermediates is described. The efficient synthesis α-quaternary allylated β-keto-esters was accomplished by the alkylation compounds. Alternatively, an unprecedented (1+4) annulation 2-(hydroxymethyl)allyl via dual catalysis also successfully developed, affording a wide variety tetrahydrofurans in good to high yields.

Язык: Английский

Процитировано

2

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

Liping Yin,

Xinyi Zhang,

B. D. Wang

и другие.

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(17), С. 3616 - 3623

Опубликована: Июнь 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.

Язык: Английский

Процитировано

0

Cesium and Phenoxide Interaction Enabled by Rh Overrides the Innate Solvent-Mediated Chemoselectivity DOI

Romin Gogoi,

Garima Jindal

ACS Catalysis, Год журнала: 2024, Номер 14(16), С. 12351 - 12358

Опубликована: Авг. 5, 2024

DLPNO-CCSD(T) calculations are carried out to understand the distinctive chemoselectivity in a Rh(II)-catalyzed carbene insertion into C(sp2)–H bond unprotected phenols without preinstalled directing groups. As per conventional rules of solvation and separated ion pair polar aprotic solvents like acetonitrile, reaction should have resulted an O–H insertion. However, our reveal transition state model that helps overriding innate acetonitrile. It involves explicit participation added Cs2CO3 base, where interaction between phenoxide oxygen Cs cation, but not as metal-bound phenoxide, is crucial for controlling chemoselectivity. Our study will be helpful developing further reactions with broad catalyst, substrate, solvent scope.

Язык: Английский

Процитировано

0