Synthesis of Janus All-Cis Tetrafluorocyclohexanes Carrying 1,4-Diether Motifs DOI Creative Commons

Thomas J. Poskin,

Bruno A. Piscelli, Aidan P. McKay

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 27, 2024

Nucleophilic aromatic substitutions (SNAr) of alkoxides on pentafluoroaryl ethers are explored as a first step in synthesis sequence to generate all-cis 2,3,5,6-tetrafluorocyclohexyl-1,4-dialkyl 1. The SNAr reaction was both experimentally and theoretically rationalize ortho/para/meta selectivities. tert-Butyl deprotection products followed by phenol alkylations introduces versatility the synthesis. final Rh(CAAC) 3 catalyzed aryl hydrogenation intermediate tetrafluoroaryl-1,4-diethers generated cyclohexane This chemistry new class Janus fluorocyclohexane derivatives with ether substituents placed 1,4- each other.

Language: Английский

Palladium-Catalyzed Site-Selective Regiodivergent Carbocyclization of Di- and Trienallenes: A Switch between Substituted Cyclohexene and Cyclobutene DOI Creative Commons
Wei‐Jun Kong, Haibo Wu, Jiayi Chen

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 6, 2025

Nature efficiently produces a myriad of structurally diverse carbon ring frameworks from common linear precursors via cyclization reactions at specific olefinic sites in dienes or polyenes. In contrast, achieving the site-selective functionalization diene polyene substrates remains formidable challenge chemical synthesis. Herein, we report pair highly site-selective, regiodivergent carbocyclization dienallenes and trienallenes, enabling efficient synthesis cis-1,4-disubstituted cyclohexenes trans-1,2-disubstituted cyclobutenes precursor with high diastereoselectivity. Remarkably, simple achiral organophosphoric acids amines are identified as powerful ligands for controlling these palladium-catalyzed carbocyclizations. This approach represents first example carbocyclization, providing practical method stereospecific thermodynamically disfavored fully substituted trans-1,2-cyclobutenes. Additionally, methodology developed offers general insights into development metal-catalyzed carbocyclizations precursors, mimicking natural processes.

Language: Английский

Citations

1
Enantioselective Cobalt-Catalyzed Remote Hydroboration of Alkenylboronates DOI
Wenke Dong,

Zheming Liu,

Aoxuan Bai

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 14, 2025

Heteroatomic groups in alkenes typically direct thermodynamically favored chain walking of C═C bonds toward themselves, thereby facilitating C-H bond functionalization near the heteroatoms. We present herein an efficient cobalt-catalyzed contra-thermodynamic remote hydroboration alkenylboronates with pinacolborane to synthesize chiral 1,n-diboronates. This protocol features a broad substrate scope, high functional group tolerance, and excellent enantioselectivity. Mechanistic studies indicate involvement chain-walking process. Gram-scale reactions various product derivatizations further highlight its practicality.

Language: Английский

Citations

0
Transforming Carbohydrates Through Multicomponent Reactions: Advances and Applications DOI
Priyank Purohit, Ravi Kumar Mittal, Prabhat Kumar Upadhyay

et al.

ChemistrySelect, Journal Year: 2025, Volume and Issue: 10(15)

Published: April 1, 2025

Abstract This review highlights multicomponent reactions (MCRs) and their utilization in carbohydrate chemistry, where the anomeric center remains a concerning point maintaining selectivity is major challenge. Successful examples included involve synthesis of multifunctional carbohydrates with enhanced inherent physicochemical biological properties. compiles presents importance MCR which parent structure modified intact. explores various types MCRs applied to carbohydrates, highlighting synthesis, derivatization, functionalization molecules. The mechanistic aspects these highlight how unique structural features influence reaction pathways outcomes. applications fields glycomics glycoproteomics are shown, extension probability also discussed here. Through this comprehensive review, we provide insights into current state art identify promising future research directions that could further enhance utility impact chemical sciences. reader will be inspired perform for complex molecule expand use materials science.

Language: Английский

Citations

0
Synthesis of Janus All-Cis Tetrafluorocyclohexanes Carrying 1,4-Diether Motifs DOI Creative Commons

Thomas J. Poskin,

Bruno A. Piscelli, Aidan P. McKay

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 27, 2024

Nucleophilic aromatic substitutions (SNAr) of alkoxides on pentafluoroaryl ethers are explored as a first step in synthesis sequence to generate all-cis 2,3,5,6-tetrafluorocyclohexyl-1,4-dialkyl 1. The SNAr reaction was both experimentally and theoretically rationalize ortho/para/meta selectivities. tert-Butyl deprotection products followed by phenol alkylations introduces versatility the synthesis. final Rh(CAAC) 3 catalyzed aryl hydrogenation intermediate tetrafluoroaryl-1,4-diethers generated cyclohexane This chemistry new class Janus fluorocyclohexane derivatives with ether substituents placed 1,4- each other.

Language: Английский

Citations

0