Catalytic 1,2-Radical Acyloxy Migration: A Strategy to Access Novel Chemical Space and Reaction Profiles DOI
Gaoyuan Zhao, Upasana Mukherjee, Wang Yao

и другие.

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Май 22, 2025

ConspectusRadical migration represents a powerful strategy for reaction discovery and development in organic synthesis, offering access to unprecedented functional molecules chemical space. In this Account, we describe our contributions the field, particularly focusing on 1,2-radical acyloxy (RAM), process involving transposition of radical an group. We highlight its application carbohydrate modification allyl carboxylate trifunctionalization, demonstrating how reactivity enables streamlined synthesis novel glycomimetics facilitates selective 1,2,3-trifunctionalization carboxylates. These advances establish 1,2-RAM as versatile platform catalytic transformations, unlocking new opportunities molecule design.Our approach leverages excited-state palladium ground-state nickel catalysis modify carbohydrates, specifically at C2 position. This C2-deoxy-hydrogenation, deuteration, iodination, alkenylation, allylation, ketonylation, arylation reactions, providing direct glycomimetics. transformations streamline structurally diverse glycomimetics, facilitating carbohydrate-based molecules. Furthermore, mild conditions high group tolerance these systems make them attractive late-stage functionalization, broadening their applicability complex synthesis.Beyond have extended achieve By employing phosphine catalysis, demonstrate 1,3-carbobromination accompanied by shift. proof-of-concept study lays foundation developing broader range effectively transforming carboxylates into substituted isopropyl donors. advancement expands synthetic utility carboxylates, enabling rapid construction molecular scaffolds.In summary, opens avenue development, granting The conditions, broad compatibility, unique it valuable tool synthesis. anticipate that merging with other platforms will further advance bond disconnection strategies, provide molecules, expand frontiers

Язык: Английский

Fluoroalkylacylsilanes as Novel Ambiphilic Donor–Acceptor Carbene Precursors DOI
Xiao Shen

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Апрель 25, 2025

ConspectusCarbenes, as highly reactive intermediates, have emerged pivotal tools in organic synthesis, catalysis, and materials science due to their versatile reactivity broad applicability. Among the diverse classes of carbenes, donor-acceptor carbenes (DACs) attracted significant attention owing unique electronic properties exceptional reaction selectivity. The distinctive DACs arises from synergistic interplay between electron-withdrawing electron-donating groups attached carbene center, enabling a wide array transformations. These attributes established indispensable building blocks for constructing complex molecular architectures achieving precise control over chemical transformation.This Account highlights our recent advancements development fluoroalkylacylsilanes novel precursors DACs. Under photocatalytic conditions, these generate fluoroalkyl siloxycarbenes via radical Brook rearrangement. group, known its strong properties, imparts electrophilic characteristics, while siloxyl group stabilizes center. Together, functionalities render ideal candidates generation DACs, providing platform range transformations, including cycloadditions, bond insertions, construction new structures.First, we developed visible-light-induced, organocatalyzed [2 + 1] cyclization alkynes trifluoroacetylsilanes, leading synthesis cyclopropenols. Mechanistic studies provided compelling evidence involvement triplet intermediates this reaction, demonstrating utility functionalized cyclic compounds. Second, explored cyclopropanation reactions elucidated diastereoselective transfer trifluoroacetylsilane-derived alkenes. Density functional theory (DFT) calculations revealed key insights into origins observed diastereoselectivity, offering molecular-level understanding stereochemical outcomes. Additionally, extended scope include organoboronic esters, divergent ketones. By modulating situ-generated organoboronate complexes─formed through with esters─we achieved selective both fluorine-maintaining defluorinated This transition-metal-free approach is operationally simple compatible substrates, aryl, alkenyl, alkyl boronic esters. Beyond C-B functionalization, applied C(sp2)-H functionalization 1,3-azoles. investigations suggest that success stems dual role trifluoroacetylsilanes under conditions: they not only participate but also produce biradicals facilitate ring-opening aromatization fused cyclopropanes.We anticipate work on ambiphilic will lay groundwork further use acylsilanes chemistry. developments are expected inspire strategies design expand silanes synthetic opening avenues intricate architectures.

Язык: Английский

Процитировано

1
Visible-Light-Induced [2 + 2] Cyclization of Alkynes with Bromodifluoroacetylsilanes: Facile Access to gem-Difluorocyclobutenones DOI
Gang Zhou, Yongpeng Li, Ying Liu

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер 147(19), С. 15955 - 15962

Опубликована: Апрель 29, 2025

Herein, we report a simple and efficient method for the synthesis of gem-difluorocyclobutenones from alkynes bromodifluoroacetylsilanes, proceeding via formal cyclization with in situ generated difluoroketene under visible-light-induced conditions. The reaction conditions are mild exhibit broad substrate scope, including both aromatic aliphatic alkynes. Additionally, demonstrates good functional group tolerance, facile scalability, potential diverse downstream transformations. Mechanistic studies suggest that bromodifluoroacetylsilanes act as photochemical precursors to difluoroketene.

Язык: Английский

Процитировано

1
Acylsilanes as Weakly Coordinating Directing Groups for Metal-Catalyzed C–H Functionalization DOI
Rowan L. Pilkington, Daniel L. Priebbenow

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 6881 - 6894

Опубликована: Апрель 14, 2025

Язык: Английский

Процитировано

0
Recent Advances in Metal-Catalyzed Transformations of Acylsilanes via the Activation of C–Si Bonds DOI
Vishal Kumar Rawat, Mamoru Tobisu

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 8706 - 8723

Опубликована: Май 8, 2025

Язык: Английский

Процитировано

0
Catalytic 1,2-Radical Acyloxy Migration: A Strategy to Access Novel Chemical Space and Reaction Profiles DOI
Gaoyuan Zhao, Upasana Mukherjee, Wang Yao

и другие.

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Май 22, 2025

ConspectusRadical migration represents a powerful strategy for reaction discovery and development in organic synthesis, offering access to unprecedented functional molecules chemical space. In this Account, we describe our contributions the field, particularly focusing on 1,2-radical acyloxy (RAM), process involving transposition of radical an group. We highlight its application carbohydrate modification allyl carboxylate trifunctionalization, demonstrating how reactivity enables streamlined synthesis novel glycomimetics facilitates selective 1,2,3-trifunctionalization carboxylates. These advances establish 1,2-RAM as versatile platform catalytic transformations, unlocking new opportunities molecule design.Our approach leverages excited-state palladium ground-state nickel catalysis modify carbohydrates, specifically at C2 position. This C2-deoxy-hydrogenation, deuteration, iodination, alkenylation, allylation, ketonylation, arylation reactions, providing direct glycomimetics. transformations streamline structurally diverse glycomimetics, facilitating carbohydrate-based molecules. Furthermore, mild conditions high group tolerance these systems make them attractive late-stage functionalization, broadening their applicability complex synthesis.Beyond have extended achieve By employing phosphine catalysis, demonstrate 1,3-carbobromination accompanied by shift. proof-of-concept study lays foundation developing broader range effectively transforming carboxylates into substituted isopropyl donors. advancement expands synthetic utility carboxylates, enabling rapid construction molecular scaffolds.In summary, opens avenue development, granting The conditions, broad compatibility, unique it valuable tool synthesis. anticipate that merging with other platforms will further advance bond disconnection strategies, provide molecules, expand frontiers

Язык: Английский

Процитировано

0