Construction of Chiral C2-Quaternary Indolines via Palladium-Catalyzed Decarboxylative Asymmetric Amination DOI

Mingjun Lv,

Xinhui Yu,

Jitian Liu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 15(1), P. 255 - 264

Published: Dec. 16, 2024

The catalytic asymmetric synthesis of functionalized C2-quaternary indoline scaffolds has garnered significant attention in organic and drug discovery due to the inherent challenges potential applications. Herein, we present a facile approach utilizing Pd-catalyzed intramolecular decarboxylative amination vinyl benzoxazepinones, leading efficient construction challenging chiral 2-vinyl-2-aryl/alkyl frameworks good yields with high enantioselectivities (>50 examples, up 83% yield 97% ee). Furthermore, these indolines can be readily scaled further modified access complex polycyclic structures. We also synthesized several indoline-based ligands that exhibit promising efficiency as catalysts reactions. Computational studies provided insight into inner-sphere mechanism.

Language: Английский

Palladium-Catalyzed Ligand-Controlled Switchable Hetero-(5 + 3)/Enantioselective [2σ+2σ] Cycloadditions of Bicyclobutanes with Vinyl Oxiranes DOI
Jin‐Lan Zhou, Yuanjiu Xiao,

Linke He

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(29), P. 19621 - 19628

Published: May 13, 2024

For nearly 60 years, significant research efforts have been focused on developing strategies for the cycloaddition of bicyclobutanes (BCBs). However, higher-order and catalytic asymmetric BCBs long-standing formidable challenges. Here, we report Pd-catalyzed ligand-controlled, tunable cycloadditions divergent synthesis bridged bicyclic frameworks. The dppb ligand facilitates formal (5+3) vinyl oxiranes, yielding valuable eight-membered ethers with scaffolds in 100% regioselectivity. Cy-DPEphos promotes selective hetero-[2σ+2σ] to access pharmacologically important 2-oxabicyclo[3.1.1]heptane (O-BCHeps). Furthermore, corresponding O-BCHeps 94–99% ee has achieved using chiral (S)-DTBM-Segphos, representing first cross-dimerization two strained rings. obtained are promising bioisosteres ortho-substituted benzenes.

Language: Английский

Citations

43
Recent Progress in (3+3) Cycloadditions of Bicyclobutanes to Access Bicyclo[3.1.1]heptane Derivatives DOI
Jian‐Jun Feng

Synlett, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 28, 2024

Abstract The synthesis of bicyclo[3.1.1]heptane (BCHeps) derivatives, which serve as three-dimensional (3D) bioisosteres benzenes and are the core skeleton several terpene natural products, is garnering growing interest. (3+3) cycloadditions bicyclobutanes (BCBs) represent an attractive method for efficiently accessing (hetero)BCHep skeletons with 100% atom economy. Herein, we give a brief summary recent achievements in this approach diverse BCHep emphasizing our progress initial palladium-catalyzed vinyl oxiranes. 1 Introduction 2 Radical Cycloaddition Reaction 3 Polar 4 Palladium-Catalyzed Enantioselective 5 Conclusion

Language: Английский

Citations

7
Catalytic transformation of carbon dioxide into seven-membered heterocycles and their domino transformation into bicyclic oxazolidinones DOI Creative Commons
Wangyu Shi, J. Benet‐Buchholz, Arjan W. Kleij

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Feb. 5, 2025

Converting carbon dioxide (CO2) into valuable heterocycles is of great synthetic value but usually limited to five- and six-membered ring compounds. Here, we report a catalytic approach for transforming this renewable seven-membered using double-stage approach, combining silver-catalyzed alkyne/CO2 coupling subsequent base-catalyzed ring-expansion. This methodology avoids the formation thermodynamically more stable, smaller-ring by-products has good functional group tolerance. The application these larger-ring cyclic carbonates further demonstrated by showing their unique ability serve as synthons preparation bicyclic oxazolidinone pharmacores through an intramolecular domino sequence that involves transient ketimine group, various other intermolecular transformations. results described herein significantly expand on use CO2 cheap versatile feedstock generating elusive pharmaceutically relevant authors heterocycles, expansion.

Language: Английский

Citations

0
Divergent Synthesis of Dihydrofuran and Dienol Scaffolds via Pd-Catalyzed Decarboxylative Carbene Cross-Coupling DOI
Xiaolong Ma,

Erfei Miao,

Yili Sun

et al.

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

Published: April 24, 2025

Herein, we report a novel ligand-switchable Pd-catalyzed carbene coupling reaction employing vinylethylene carbonates and sulfoxonium ylides. By proper choice of ligands, the chemoselectivity process could be efficiently regulated, allowing for availability dihydrofuran or dienol scaffolds. This method features mild conditions, broad scope, remarkable synthetic utility. Compound 6f can effectively stimulate secretion GLP-1, providing promising insight into development small-molecule agonists GLP-1 receptor.

Language: Английский

Citations

0
Ligand-controlled divergent asymmetric C(sp3)−H and C(sp3)−O insertion via vinyl cations DOI Creative Commons

Cui‐Ting Li,

Li‐Gao Liu,

Jia-Zheng Li

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: May 2, 2025

The insertion of either C-H bond or C-O via cleavage has proven to be a very attractive strategy for the construction C-C and bonds in organic synthesis. However, such divergent catalytic asymmetric reactions selective formation C(sp3)-H formal C(sp3)-O products from same precursors are rarely explored. Herein, we report ligand-controlled reaction vinyl cations by non-diazo approach, leading practical atom-economical assembly range chiral spiro fused polycyclic pyrroles generally moderate excellent yields with chemo- enantioselectivities. Importantly, this protocol not only represents rare example successful reaction, but also constitutes an enantioselective 1,6-C-H carbenoid into acetals approach.

Language: Английский

Citations

0
Pd-Catalyzed Three-Component Coupling of Cyclopropenones via Sequential C–C Bond Activation and Allylation DOI
Zhou Zhang,

Feifei Liang,

Shulin Zhang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(20), P. 4262 - 4267

Published: May 9, 2024

A novel Pd-catalyzed three-component domino reaction for the stereoselective synthesis of highly functionalized allyl cinnamates has been developed. In this protocol, a sequential process C–C bond activation and intermolecular allylic substitution was well-organized. The key transformation is in situ generated hydrolysis product cyclopropenone, which triggered new with vinylethylene carbonates. mechanism investigated, demonstrating high stereoselectivity excellent atomic economy process.

Language: Английский

Citations

3
Photoredox-catalyzed oxytrifluoromethylation of alkenes toward CF3-containing five-membered cyclic carbonates DOI

Yihui Mao,

X.‐S. Wang,

Chengcheng Zhong

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(16), P. 4464 - 4469

Published: Jan. 1, 2024

A visible-light-induced oxytrifluoromethylation reaction of carbamate-containing alkenes has been reported for the synthesis diverse cyclic carbonates and vicinal diols bearing trifluoroethyl substituted quaternary centers.

Language: Английский

Citations

1
Cu-Catalyzed Asymmetric Synthesis of γ-Amino Alcohols Featuring Tertiary Carbon Stereocenters DOI Creative Commons
Alejandro Delgado, P. Orlando, Matteo Lanzi

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 30, 2024

Alkyne-functionalized oxetanes are presented as versatile substrates that in combination with amine reagents can be transformed into structurally diverse, chiral γ-amino alcohols featuring a tetrasubstituted tertiary stereocenter under Cu catalysis. Control experiments demonstrate the privileged nature of these oxetane precursors terms yield and asymmetric induction levels developed protocol, postsynthetic modifications offer an easy way to access more advanced synthons.

Language: Английский

Citations

1
Chemo‐, Regio‐ and Stereoselective Preparation of (Z)‐2‐Butene‐1,4‐Diol Monoesters via Pd‐Catalyzed Decarboxylative Acyloxylation DOI
Cheng Long,

Jiali Zhao,

Xiaotian Zhang

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(39)

Published: May 13, 2024

(Z)-alkenes are useful synthons but thermodynamically less stable than their (E)-isomers and typically more difficult to prepare. The synthesis of 1,4-hetero-bifunctionalized is particularly challenging due the inherent regio- stereoselectivity issues. Herein we demonstrate a general, chemoselective direct (Z)-2-butene-1,4-diol monoesters. protocol operates within Pd-catalyzed decarboxylative acyloxylation regime involving vinyl ethylene carbonates (VECs) various carboxylic acids as reaction partners under mild operationally attractive conditions. newly developed process allows access structurally diverse pool monoesters in good yields with excellent stereoselectivity. Various synthetic transformations obtained how these great use rapidly diversify portfolio formal desymmetrized (Z)-alkenes.

Language: Английский

Citations

0
Direct synthesis of spirooxindoles enabled by palladium-catalyzed allylic alkylation and DBU-mediated cyclization: concept, scope and applications DOI

Fen Tan,

Xiaoyu He,

Qiao-Qiao Zhou

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(19), P. 5443 - 5453

Published: Jan. 1, 2024

A concise construction of spiro[indoline-3,2′-pyrrol]-2-one skeletons is reported. This reaction proceeded through a palladium-catalyzed decarboxylative allylic alkylation followed by DBU-mediated intramolecular cyclization.

Language: Английский

Citations

0