Rhodium(II)-Catalyzed Strain-Enabled Stereoselective Synthesis of Skipped Dienes DOI
Ganesh Arjun Kadam, Tushar Singha,

Sapna Rawat

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(16), P. 12225 - 12233

Published: Aug. 1, 2024

Skipped dienes are not only present in fatty acid primary metabolites and natural products but also serve as reactive intermediates diverse chemical synthesis. Despite this, the regioselective stereoselective synthesis of skipped remains a challenging goal. Strain release organic molecules is powerful tool for creating complexity under mild conditions. The reactivity strained bicyclo[1.1.0]butane (BCB) systems mainly dominated by transformations relying on their innate electrophilic reactivity. Herein, we report rare example carbene-type BCB system based rhodium–carbene chemistry, which enables highly through strain release. reaction compatible with range functional groups both diazo compounds BCBs could be applied successfully to complex structures, providing valuable functionalizable dienes. introduced during served synthetic handles downstream manipulations. high stereoselectivity observed has been rationalized DFT calculations, suggests that likely proceeding via concerted mechanism, noncovalent interactions between metallocarbene control exclusive selectivity.

Language: Английский

Stereoselective Radical Acylfluoroalkylation of Bicyclobutanes via N‐Heterocyclic Carbene Catalysis DOI

Chuyu Xiao,

Jing‐Ran Shan,

Wen‐Deng Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 14, 2024

Cyclobutanes are prominent structural components in natural products and drug molecules. With the advent of strain-release-driven synthesis, ring-opening reactions bicyclo[1.1.0]butanes (BCBs) provide an attractive pathway to construct these three-dimensional structures. However, stereoselective difunctionalization central C-C σ-bonds remains challenging. Reported herein is a covalent-based organocatalytic strategy that exploits radical NHC catalysis achieve diastereoselective acylfluoroalkylation BCBs under mild conditions. The Breslow enolate acts as single electron donor provides NHC-bound ketyl with appropriate steric hindrance, which effectively distinguishes between two faces transient cyclobutyl radicals. This operationally simple method tolerates various fluoroalkyl reagents common functional groups, providing straightforward access polysubstituted cyclobutanes (75 examples, up >19 : 1 d.r.). combined experimental theoretical investigations this system confirm formation NHC-derived understanding how radical-radical coupling occurs.

Language: Английский

Citations

3
Solvent‐Dependent Divergent Cyclization of Bicyclo[1.1.0]butanes DOI Creative Commons
Fuhao Zhang, Subhabrata Dutta, Alessia Petti

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 17, 2024

Bicyclo[1.1.0]butanes (BCBs) have recently garnered significant research interest as versatile precursors for synthesizing potential [n.1.1] bioisosteres and multi-functionalized cyclobutanes in a straightforward atom-economical manner. Here, we report solvent-dependent divergent cyclization of BCBs that provides highly diastereospecific decorated oxygen-containing bicyclo[3.1.1]heptanes (BCHeps), which serve meta-substituted arenes. Additionally, an unprecedented 1,2-difunctionalization reaction mode was explored, thus expanding the chemical space arene functionalized cyclobutanes.

Language: Английский

Citations

3
Asymmetric synthesis of atropisomers featuring cyclobutane boronic esters facilitated by ring-strained B-ate complexes DOI Creative Commons

Yu-Wen Sun,

Jingkun Zhao,

Xinyu Yan

et al.

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

Published: Dec. 30, 2024

The strain-release-driven reactions of bicyclo[1.1.0]butanes (BCBs) have received significant attention from chemists. Notably, 1,2-migratory enabled by BCB-derived B-ate complexes effectively complement the initiated common BCBs. desired products are particularly valuable for late-stage transformations due to presence C-B bond. However, asymmetric mediated boronate progressed slowly. In this study, we develop an synthesis atropisomers featuring cis-cyclobutane boronic esters facilitated 1,2-carbon or boron migration ring-strained complexes, achieving high enantioselectivity. reaction is compatible with various aryl, alkenyl, alkyl and B

Language: Английский

Citations

3
Oxidative Difunctionalization of N-Aryl Bicyclobutyl Amides with Aldehydes: Divergent Synthesis of Acylated and Alkylated 3-Spirocyclobutyl Oxindoles DOI
Pengfei Xia, Jiao Zhou,

Jing Yuan

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(30), P. 6486 - 6490

Published: July 23, 2024

An efficient and operationally simple oxidative radical difunctionalization of

Language: Английский

Citations

2
Rhodium(II)-Catalyzed Strain-Enabled Stereoselective Synthesis of Skipped Dienes DOI
Ganesh Arjun Kadam, Tushar Singha,

Sapna Rawat

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(16), P. 12225 - 12233

Published: Aug. 1, 2024

Skipped dienes are not only present in fatty acid primary metabolites and natural products but also serve as reactive intermediates diverse chemical synthesis. Despite this, the regioselective stereoselective synthesis of skipped remains a challenging goal. Strain release organic molecules is powerful tool for creating complexity under mild conditions. The reactivity strained bicyclo[1.1.0]butane (BCB) systems mainly dominated by transformations relying on their innate electrophilic reactivity. Herein, we report rare example carbene-type BCB system based rhodium–carbene chemistry, which enables highly through strain release. reaction compatible with range functional groups both diazo compounds BCBs could be applied successfully to complex structures, providing valuable functionalizable dienes. introduced during served synthetic handles downstream manipulations. high stereoselectivity observed has been rationalized DFT calculations, suggests that likely proceeding via concerted mechanism, noncovalent interactions between metallocarbene control exclusive selectivity.

Language: Английский

Citations

2