Highly Diastereoselective Radical Cyclopropanation of Olefins via Cobaloxime‐Based Metalloradical Catalysis DOI Open Access
Liming Tan, McKay Boehme,

Lorenzo Papworth

et al.

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

Published: Nov. 7, 2024

Abstract Metalloradical catalysis (MRC), predominantly exemplified by metalloporphyrin complexes, has emerged as a promising strategy for regulating radical reactions and broadening their synthetic applications. In this paper, we report that cobaloxime functioning surrogate systems, can mediate cyclopropanation of olefins using donor/acceptor‐type carbene precursor α‐aryl diazoacetates through the MRC process. The reaction proceeds under mild conditions, yielding cyclopropane derivatives in good yields with high diastereoselectivity. exhibits extensive substrate tolerance, encompassing gram‐scale transformations synthesis pharmaceutical compounds. Our discoveries underscore potential cobaloxime‐catalyzed valuable asset organic syntheses further expand repertoire metalloradical systems catalysis.

Language: Английский

Biomimetic Photoexcited Cobaloxime Catalysis in Organic Synthesis DOI Creative Commons
Phong Dam, Kaiming Zuo, Luis Miguel Azofra

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(33)

Published: May 22, 2024

Abstract Drawing inspiration from nature has long been a cornerstone of chemical innovation, with natural systems offering wealth untapped potential for discovery. In this minireview, we delve into the burgeoning field cobaloxime catalysis in organic synthesis, which mimics catalytic activity organometallic alkylcobalamine enzymes. Our focus lies on elucidating latest advancements area, as well delineating primary mechanistic pathways at play. By describing, and comparing these mechanisms, provide comprehensive overview current state‐of‐the‐art, while also shedding light key unresolved challenges that await further exploration.

Language: Английский

Citations

13
Visible Light-Induced Cobalt-Catalyzed 1,3-Diphosphination of Alkenes DOI
Wenlong Shan, Zemin Wang,

Chenxia Gao

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(18), P. 9749 - 9756

Published: Jan. 1, 2024

A novel cobalt-catalyzed radical 1,3-diphosphination of alkenes was developed, which enables straightforward access to 1,3-diphosphine skeleton compounds under mild conditions.

Language: Английский

Citations

5
Biomimetic Dehydrogenative Intermolecular Formal Allylic Amidation of Branched α‐Olefins DOI Creative Commons
Xiaoyang Fu,

Jiarui Tian,

Mingjun Zhang

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: 12(2)

Published: Nov. 18, 2024

Abstract Allylic amide moieties are commonly encountered in natural products and privileged structures pharmaceuticals agrochemicals. Moreover, because allylic can be to converted into an array of high‐value motifs, they have been widely employed organic synthesis. However, the development catalytic systems for intermolecular amidation olefins, particularly branched α ‐olefins, has proven challenging. Here, a biomimetic, synergistic method is reported that combines photoredox, cobalt, Brønsted base catalysis synthesis substituted amides from ‐olefins simple imides without using oxidants. This low‐cost, operationally features broad substrate scope excellent functional group compatibility. it successfully used functionalization several structurally complex molecules demonstrating method's potential utility medicinal chemistry applications. Mechanistic studies revealed C( sp 3 )─N bond formation mediated by nitrogen‐centered radical intermediate, which generated via sequence involving deprotonation single‐electron oxidation.

Language: Английский

Citations

4
Copper-catalyzed C–N cross-coupling for construction of alkylated N-cyanamide derivatives via nitrogen umpolung DOI
Yanjun Wan,

Harriet K. Zhang,

Jin Qian

et al.

Chem, Journal Year: 2024, Volume and Issue: 10(8), P. 2538 - 2549

Published: May 21, 2024

Language: Английский

Citations

2
Visible‐Light‐Driven Formyl Group Migration Triggered Remote Desaturation DOI

Yuwei Hong,

Yizhou Qin,

Xiong Yang

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(28)

Published: May 10, 2024

Abstract Dehydrogenation of unactivated alkanes to form versatile alkenes is an important but challenging task in synthetic chemistry. Enabled by a radical‐mediated formyl group migration, novel visible light‐induced remote desaturation aldehydes developed, delivering panel trifluoromethylated δ,ϵ‐ or γ,δ‐unsaturated moderate excellent yields with good functional tolerance at room temperature. Mechanistic studies indicate reaction pathway comprising the cascade trifluoromethylation C−C double bonds, intramolecular addition aldehydes, β‐fragmentation alkoxy radicals, single electron transfer oxidation, and deprotonation. It provides complementary approach existing protocols.

Language: Английский

Citations

0
Biomimetic Photoexcited Cobaloxime Catalysis in Organic Synthesis DOI Creative Commons
Phong Dam, Kaiming Zuo, Luis Miguel Azofra

et al.

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

Published: May 22, 2024

Abstract Drawing inspiration from nature has long been a cornerstone of chemical innovation, with natural systems offering wealth untapped potential for discovery. In this minireview, we delve into the burgeoning field cobaloxime catalysis in organic synthesis, which mimics catalytic activity organometallic alkylcobalamine enzymes. Our focus lies on elucidating latest advancements area, as well delineating primary mechanistic pathways at play. By describing, and comparing these mechanisms, provide comprehensive overview current state‐of‐the‐art, while also shedding light key unresolved challenges that await further exploration.

Language: Английский

Citations

0
Highly Diastereoselective Radical Cyclopropanation of Olefins via Cobaloxime‐Based Metalloradical Catalysis DOI Open Access
Liming Tan, McKay Boehme,

Lorenzo Papworth

et al.

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

Published: Nov. 7, 2024

Abstract Metalloradical catalysis (MRC), predominantly exemplified by metalloporphyrin complexes, has emerged as a promising strategy for regulating radical reactions and broadening their synthetic applications. In this paper, we report that cobaloxime functioning surrogate systems, can mediate cyclopropanation of olefins using donor/acceptor‐type carbene precursor α‐aryl diazoacetates through the MRC process. The reaction proceeds under mild conditions, yielding cyclopropane derivatives in good yields with high diastereoselectivity. exhibits extensive substrate tolerance, encompassing gram‐scale transformations synthesis pharmaceutical compounds. Our discoveries underscore potential cobaloxime‐catalyzed valuable asset organic syntheses further expand repertoire metalloradical systems catalysis.

Language: Английский

Citations

0