Photoexcited Palladium-Catalyzed Synthesis of Chiral Allenes from Alkynes via Isomerization and Deracemization Sequence DOI

Changhua Song,

Shouyun Yu

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(21), P. 15997 - 16002

Published: Oct. 16, 2024

A photoexcited palladium-catalyzed synthesis of chiral allenes from alkynes via a sequence isomerization and deracemization is disclosed. This method offers an efficient cost-effective approach to produce wide range with good enantioselectivities yields (up 98% yield 99% ee). The use readily available stable as starting materials simplifies experimental procedures broadens the scope allene synthesis. DBU plays crucial dual role in this reaction effectively facilitate enhance under visible light excitation, both which are vital for success process.

Language: Английский

Total Synthesis of Principinol B DOI
Qiang Du,

Zhibo Fan,

Ming Yang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(17)

Published: Feb. 23, 2024

We have accomplished the first and asymmetric total synthesis of principinol B, a grayanoid possessing an oxabicyclo[3.2.1] architecture. A functionalized 5/7/6/5 tetracyclic intermediate was assembled in convergent manner by diastereoselective intermolecular aldol reaction subsequent carbonyl-olefin metathesis two enantiomerically enriched fragments. The architecture containing 6,10-ether bridge constructed Williamson ether synthesis.

Language: Английский

Citations

10
Skeletal Editing of Benzene Motif: Photopromoted Transannulation for Synthesis of DNA-Encoded Seven-Membered Rings DOI
Yue Zhang,

Jia‐ying Xue,

Xiao‐can Su

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(11), P. 2212 - 2217

Published: March 7, 2024

In this report, we present a photopromoted, metal-free transannulation of phenyl azides for the synthesis DNA-encoded seven-membered rings. The transformation is efficiently achieved through skeletal editing strategy targeting benzene motif coupled with Reversible Adsorption to Solid Support (RASS) strategy. A variety valuable ring compounds, including 3H-azepines, azepinones, and unnatural amino acids, are now accessible. Crucially, DNA-compatible protocol can also be applied introduction complex molecules, as exemplified by Lorcaserin Betahistine. selective conversion readily available rings into high-value offers promising avenue construction diversified drug-like library.

Language: Английский

Citations

5
Successive energy-transfer catalytic dearomative reactions of quinolines with bicyclo[1.1.0]butanes for the synthesis of pyridine-fused 3D complicated molecules DOI Creative Commons
Cai Yiping, Shi Chen, Qin‐Hua Song

et al.

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Successive energy-transfer-mediated dearomative [2π + 2σ] cycloaddition/1,6-HAT cascade reaction of quinolines with bicyclo[1.1.0]butanes provides a facile synthesis pyridine-fused 3D complicated molecules.

Language: Английский

Citations

0
Construction of the Tetracyclic Skeleton of Polycyclic Norcembranoids Sinudenoids B–D Via Ireland-Claisen Rearrangement DOI
Xiaofei Gao, Hui Shen, Peng Chen

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 20, 2025

Sinudenoids B-D represent a biologically significant and structurally intricate family of natural products distinguished by their unique [5-5-6-6] tetracyclic skeleton. Herein, we present an efficient strategy for the asymmetric synthesis framework. Key features our approach include convergent synthetic driven esterification, pivotal Ireland-Claisen rearrangement to construct C11-C12 bond, followed lactonization isomerization, ring-closing metathesis complete

Language: Английский

Citations

0
Stereoselective Synthesis of the Core Ring System of Lancifonins A–D DOI
Lu Guo, Kaishun Bi,

Tengying Chen

et al.

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

Published: March 24, 2025

A 5/5/7 tricyclic intermediate bearing an oxa-bridged hemiketal ring was successfully synthesized from dihydrocarvone in 14 steps, which is a common of various Schisandra nortriterpenoids. Subsequently, the core structure lancifonins A–D, characterized by 5/5/7/8 fused system, constructed seven steps. The route employs key transformations, including aldol reaction, Mukaiyama hydration, Mn(III)-mediated cyclization, Suzuki and McMurry coupling.

Language: Английский

Citations

0
Base-Mediated Synthesis of Imidazole-Fused 1,4-Benzoxazepines via 7-exo-dig Cyclizations: Propargyl Group Transformation DOI Creative Commons

Nalan Korkmaz Cokol,

Fevzi Can Inyurt,

I. Ferit Öktem

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 26, 2025

Herein, we describe the synthesis of a series imidazole-fused 1,4-benzoxazepines using 7-exo-dig cyclizations. Two sets substrates, one containing disubstituted alkyne functional groups and other featuring terminal alkynes, were synthesized by O-propargylation, Sonogashira cross-coupling, condensation reactions between aldehydes o-diaminobenzene. While substrates yielded exocyclic E/Z configured cyclization products smoothly, involving alkynes resulted in formation isomeric with altered skeletal structures, addition to expected products. Density theory (DFT) calculations used clarify mechanisms underlying these It is suggested that unexpected are formed through intermolecular O-to-N-propargyl transfer reactions, followed cyclization, accordance Baldwin's rules. Furthermore, this study extensively demonstrates conversion endocyclic base-mediated 1,3-H shift.

Language: Английский

Citations

0
Allylic Acetal as 3C Synthon in Rh(III)-Catalyzed Divergent C–H Activation/[4 + 3] Annulation: Easy Access to Benzodiazepines DOI
Mingming Hu, Chao Pi, Yangjie Wu

et al.

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

Published: April 2, 2025

A concise synthesis of benzodiazepines via Rh(III) catalyzed C-H activation/ [4 + 3] annulation easily available 1-arylpyrazolidinones with allylic acetal has been developed. The was employed as a novel 3C synthon in this transformation. Benzodiazepines were built under mild reaction conditions high efficiency and chemoselectivity. atom-economy accessible substrates reveal potential application.

Language: Английский

Citations

0
Mechanistic insights into facilitating reductive elimination from Ni(ii) species DOI

Bolin Qiao,

Fa-You Lin,

Dongmin Fu

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(62), P. 8008 - 8019

Published: Jan. 1, 2024

Reductive elimination is a key step in Ni-catalysed cross-couplings, which often considered to result new covalent bonds. Due the weak oxidizing ability of Ni(II) species, reductive eliminations from centers are challenging. A thorough mechanistic understanding this process could inspire rational design coupling reactions. In article, we give an overview recent advances study species achieved by our group. Three possible models for were investigated and discussed, including direct elimination, electron density-controlled oxidation-induced elimination. Notably, requires high activation energy some cases. contrast, pathways can significantly enhance driving force accelerating formation The intricate reaction mechanisms each these thoroughly discussed systematically summarized paper. These computational studies showcase characteristics three hope that it will spur development cross-coupling

Language: Английский

Citations

2
Base-Promoted (5 + 2) Annulation between 2-(Alkynylaryl)acetonitriles and Arylalkynes for the Synthesis of Benzocycloheptene Derivatives DOI
Jiatian Li,

Xiangwen Tan,

Huanfeng Jiang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(26), P. 5409 - 5414

Published: June 24, 2024

Herein, we describe a novel approach to the synthesis of benzocycloheptene derivatives via base-promoted (5 + 2) annulation between 2-(alkynylaryl)acetonitriles and arylalkynes. In this chemistry, are employed as new C5 synthon construct various benzocycloheptene(s) by building two C-C bonds in one single step. This method features excellent regioselectivity, use readily available starting materials, good functional group tolerance. The practicality strategy was further demonstrated gram-scale synthesis, late-stage functionalizations, post-modification natural products such probenecid tetrahydrofurfuryl alcohol.

Language: Английский

Citations

1
Total Synthesis of Principinol B DOI
Qiang Du,

Zhibo Fan,

Ming Yang

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(17)

Published: Feb. 23, 2024

Abstract We have accomplished the first and asymmetric total synthesis of principinol B, a grayanoid possessing an oxabicyclo[3.2.1] architecture. A functionalized 5/7/6/5 tetracyclic intermediate was assembled in convergent manner by diastereoselective intermolecular aldol reaction subsequent carbonyl–olefin metathesis two enantiomerically enriched fragments. The architecture containing 6,10‐ether bridge constructed Williamson ether synthesis.

Language: Английский

Citations

0