Mn(I)-catalyzed sigmatropic rearrangement of β, γ-unsaturated alcohols DOI Creative Commons
Can Yang, Xiaoyu Zhou,

Lixing Shen

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: April 3, 2023

Sigmatropic rearrangement provides a versatile strategy to site-selectively reorganize carbon-skeleton with high atom- and step-economy. Herein, we disclose Mn(I)-catalyzed sigmatropic of β, γ-unsaturated alcohols via C-C σ bond activation. A variety α-aryl-allylic α-aryl-propargyl could undergo in-situ 1,2- or 1,3- rearrangements allow for converting complex structural arylethyl- arylvinyl- carbonyl compounds under simple catalytic system. More importantly, this catalysis model can be further applied assemble macrocyclic ketones through bimolecular [2n + 4] coupling-cyclization monomolecular [n 1] ring-extension. The presented skeleton would useful tool complementary the traditional molecular rearrangement.

Language: Английский

Molybdenum‐Catalyzed Deoxygenative Cyclopropanation of 1,2‐Dicarbonyl or Monocarbonyl Compounds DOI
Liya Cao,

Jian‐Nan Luo,

Jiasheng Yao

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(28), P. 15254 - 15259

Published: April 26, 2021

Abstract The transition‐metal‐catalyzed cyclopropanation of alkenes by the decomposition diazo compounds is a powerful and straightforward strategy to produce cyclopropanes, but tempered potentially explosive nature substrates. Herein we report Mo‐catalyzed regiospecific deoxygenative readily available bench‐stable 1,2‐dicarbonyl compounds, in which one two carbonyl groups acts as carbene equivalent upon deoxygenation engages subsequent process. use commercially Mo catalyst afforded an array valuable cyclopropanes with exclusive regioselectivity up 90 % yield. synthetic utility this method was further demonstrated gram‐scale syntheses, late‐stage functionalization, simple monocarbonyl compound. Preliminary mechanistic studies suggest that phosphine (or silane) both mild reductant good oxygen acceptor efficiently regenerates catalytically active through reduction Mo‐oxo complexes.

Language: Английский

Citations

33
Enantioselective para‐C(sp2)−H Functionalization of Alkyl Benzene Derivatives via Cooperative Catalysis of Gold/Chiral Brønsted Acid** DOI

Xun‐Shen Liu,

Zhiqiong Tang,

Zhi‐Yao Si

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(40)

Published: Aug. 4, 2022

Abstract An asymmetric para‐ C(sp 2 )−H bond functionalization of alkyl benzene derivatives was successfully developed via cooperative catalysis gold and chiral phosphoric acid (CPA), leading to synthetically useful 1,1‐diaryl motifs. Chiral acid, ligand, molecular sieves were found be crucial for enantioselectivity control this transformation. The salient features protocol include mild conditions, high efficiency, commercially available starting materials, highly chemo‐ site‐ as well enantioselective aromatic C−H functionalization, broad substrate scope, extensive applications the products. mechanistic studies suggested that two CPAs might involved in induction.

Language: Английский

Citations

26
Gold(I)‐Catalyzed Benzylic C(sp3)−H Functionalizations: Divergent Synthesis of Indole[a]‐ and [b]‐Fused Polycycles** DOI
Luca C. Greiner, Norihito Arichi, Shinsuke Inuki

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(3)

Published: Oct. 18, 2022

Abstract Phenyl azides substituted by an (alkylphenyl)ethynyl group facilitate benzylic sp 3 (C−H) functionalization in the presence of a JohnPhosAu catalyst, resulting indole‐fused tetra‐ and pentacycles via divergent N ‐ or C ‐cyclization. The chemoselectivity is influenced depending on counter‐anion, electron density α‐imino gold(I) carbene, alkyl groups stabilizing carbocation originating from 1,5‐hydride shift. An isotopic labeling experiment demonstrates involvement indolylgold(I) species tautomerization that much faster than deauration. formation leading to seven‐membered ring also demonstrated.

Language: Английский

Citations

26
Generation and Utility of Cyclic Dienyl Gold Carbene Intermediates DOI
Cheng Zhang,

Kemiao Hong,

Shanliang Dong

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(7), P. 4646 - 4655

Published: March 22, 2023

Exploration of intermediates that enable chemo- and stereoselective cycloaddition reactions for the expeditious construction fused- bridged-ring systems continues to draw a great deal interest from synthetic community. Vinylcarbene intermediates, which serve as 1- or 3-carbon building blocks, have been frequently used cyclic frameworks through successive formation multiple carbon–carbon or/and carbon–heteroatom bonds. Here, we present concise strategy catalytic generation dienyl gold carbene species (Au-CDC) via selective gold-promoted diazo-enyne carbocyclization process. Following cycloadditions these in situ formed with different types dipolarophiles are disclosed, producing diverse array fused bridged skeletons high stereoselectivity. This method provides tool resulting straightforward access ring structural complexity diversity, is substantial complementary protocol existing methods relying on using open-chained vinylcarbene species. The subsequent exploration generated cyclopentadiene motifs accessing targets polycyclic structures can further increase this rings-per-operation count, leading conceptually Au-CDC key bridge capable connecting back-to-back cycloadditions.

Language: Английский

Citations

13
Mn(I)-catalyzed sigmatropic rearrangement of β, γ-unsaturated alcohols DOI Creative Commons
Can Yang, Xiaoyu Zhou,

Lixing Shen

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: April 3, 2023

Sigmatropic rearrangement provides a versatile strategy to site-selectively reorganize carbon-skeleton with high atom- and step-economy. Herein, we disclose Mn(I)-catalyzed sigmatropic of β, γ-unsaturated alcohols via C-C σ bond activation. A variety α-aryl-allylic α-aryl-propargyl could undergo in-situ 1,2- or 1,3- rearrangements allow for converting complex structural arylethyl- arylvinyl- carbonyl compounds under simple catalytic system. More importantly, this catalysis model can be further applied assemble macrocyclic ketones through bimolecular [2n + 4] coupling-cyclization monomolecular [n 1] ring-extension. The presented skeleton would useful tool complementary the traditional molecular rearrangement.

Language: Английский

Citations

13