Pd-catalyzed Stereodivergent [4+2] Annulation to Access [6.7]-Fused N-Heterocycles DOI
Yuan Huang,

Zhan-Cai Ma

Synlett, Journal Year: 2023, Volume and Issue: 35(12), P. 1338 - 1344

Published: Sept. 29, 2023

Abstract Stereodivergent synthesis of N-heterocycle frameworks bearing 1,3-nonadjacent stereogenic centers through a single transformation remains high-priority challenge in organic synthesis. Herein, we highlight our recent discovery stereodivergent access to such useful structural motifs using Pd-catalyzed [4+2] annulation reactions vinyl benzoxazinaones and seven-membered cyclic N-sulfonyl aldimines. A wide range N-heterocycles with were obtained high efficiency stereodivergency. Importantly, the polarity solvents was found play key role switching diastereoselectivity. Furthermore, good enantioselectivities these achieved by employment commercially available Wingphos as chiral ligand.

Language: Английский

Recent advances in ligand-enabled palladium-catalyzed divergent synthesis DOI
Yue Wang,

Jinzan Feng,

Er‐Qing Li

et al.

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 22(1), P. 37 - 54

Published: Nov. 27, 2023

Developing efficient and straightforward strategies to rapidly construct structurally distinct diverse organic molecules is one of the most fundamental tasks in synthesis, drug discovery materials science. In recent years, divergent synthesis functional from same starting has attracted significant attention been recognized as an powerful strategy. To achieve this objective, proper adjustment reaction conditions, such catalysts, solvents, ligands, etc., required. review, we summarized efforts chemo-, regio- stereodivergent reactions involving acyclic cyclic systems catalyzed by palladium complexes. Meanwhile, types, including carbonylative reactions, coupling cycloaddition well probable mechanism have also highlighted detail.

Language: Английский

Citations

14
Stereodivergent Synthesis of Spiroaminals via Chiral Bifunctional Hydrogen Bonding Organocatalysis DOI

Prasenjit Gayen,

Suman Sar,

Prasanta Ghorai

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(22)

Published: April 2, 2024

Spiroaminals represent novel structural motifs prevalent in diverse natural products and biologically active molecules. Achieving their enantioselective synthesis is a highly desirable challenging task synthetic endeavors due to intricate molecular frameworks. Herein, we accomplished the first stereodivergent construction of spiroaminals using chiral bifunctional organocatalyzed intramolecular 1,2-addition followed by an oxa-Michael addition cascade high atom step economical pathway. A proper modulation cinchona-derived squaramide catalysts efficiently provided access all possible stereoisomers with yield, diastereoselectivity, excellent enantioselectivity while displaying broad substrate tolerance. Additionally, validated scalability reaction demonstrated variable spiroaminal scaffolds, confirming viability our protocol.

Language: Английский

Citations

5
Simultaneous Stereoinvertive and Stereoselective C(sp3)–C(sp3) Cross-Coupling of Boronic Esters and Allylic Carbonates DOI Creative Commons

Hong‐Cheng Shen,

Ze‐Shu Wang, Adam Noble

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(20), P. 13719 - 13726

Published: May 9, 2024

With increasing interest in constructing more three-dimensional entities, there has been growing cross-coupling reactions that forge C(sp3)–C(sp3) bonds, which leads to additional challenges as it is not just a difficult bond construct but issues of stereocontrol also arise. Herein, we report the stereocontrolled enantioenriched boronic esters with racemic allylic carbonates enabled by iridium catalysis, leading formation bonds single or vicinal stereogenic centers. The method shows broad substrate scope, enabling primary, secondary, and even tertiary be employed, can used prepare any four possible stereoisomers coupled product chiral new method, combines simultaneous enantiospecific reaction nucleophile enantioselective electrophile process, offers solution for stereodivergent two C(sp3) fragments.

Language: Английский

Citations

5
3-Chloropropylbis(catecholato)silicate as a Bifunctional Reagent for the One-Pot Synthesis of Tetrahydroquinolines from o-Bromosulfonamides DOI Creative Commons

Noah Brodsky,

Nidheesh Phadnis,

M. K. A. IBRAHIM

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(6), P. 4191 - 4198

Published: Feb. 27, 2024

Bis(catecholato)silicate salts are easily accessible reagents that can be used to install alkyl fragments through photoredox-enabled cross-coupling. These incorporate various functional groups including pendant halides. A halogenated organosilicate reagent was leveraged develop a one-pot synthesis of tetrahydroquinolines from o-bromosulfonamides, where the bifunctional participates in nickel/photoredox cross-coupling followed by intramolecular nucleophilic substitution. The group tolerance this strategy allowed for preparation series substituted tetrahydroquinolines.

Language: Английский

Citations

2
Stereodivergent Synthesis of Spiroaminals via Chiral Bifunctional Hydrogen Bonding Organocatalysis DOI

Prasenjit Gayen,

Suman Sar,

Prasanta Ghorai

et al.

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

Published: April 2, 2024

Abstract Spiroaminals represent novel structural motifs prevalent in diverse natural products and biologically active molecules. Achieving their enantioselective synthesis is a highly desirable challenging task synthetic endeavors due to intricate molecular frameworks. Herein, we accomplished the first stereodivergent construction of spiroaminals using chiral bifunctional organocatalyzed intramolecular 1,2‐addition followed by an oxa‐Michael addition cascade high atom step economical pathway. A proper modulation cinchona‐derived squaramide catalysts efficiently provided access all possible stereoisomers with yield, diastereoselectivity, excellent enantioselectivity while displaying broad substrate tolerance. Additionally, validated scalability reaction demonstrated variable spiroaminal scaffolds, confirming viability our protocol.

Language: Английский

Citations

1
Palladium-Catalyzed (3+2) and (4+2) Cycloaddition Reactions of Sulfamidate Imine-Derived Azadienes: Synthesis of Spirocyclic Pyrrolidines and Tetrahydroquinolines DOI
Chi Bong Eric Chao, Quoc Hoang Pham, Christopher Richardson

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(18), P. 13744 - 13755

Published: Aug. 29, 2024

Diastereoselective Pd-catalyzed (3+2) and (4+2) cycloaddition reactions of sulfamidate imine-derived 1-azadienes with zwitterionic N-dipoles derived from 1-tosyl-2-vinylaziridine 4-vinylbenzoxazinone have been developed. These provide highly functionalized azaspirocycles featuring three contiguous stereocenters. The sulfonyl imine moiety the cycloadducts can be fully reduced to access valuable β-amino alcohols.

Language: Английский

Citations

0
Ligand-induced stereodivergent synthesis of spirocycles via Pd-catalyzed [4+2] annulations DOI Creative Commons

Youbin Peng,

Xiaohong Huo, Wanbin Zhang

et al.

Chem Catalysis, Journal Year: 2023, Volume and Issue: 3(7), P. 100673 - 100673

Published: July 1, 2023

Language: Английский

Citations

1
Pd-catalyzed Stereodivergent [4+2] Annulation to Access [6.7]-Fused N-Heterocycles DOI
Yuan Huang,

Zhan-Cai Ma

Synlett, Journal Year: 2023, Volume and Issue: 35(12), P. 1338 - 1344

Published: Sept. 29, 2023

Abstract Stereodivergent synthesis of N-heterocycle frameworks bearing 1,3-nonadjacent stereogenic centers through a single transformation remains high-priority challenge in organic synthesis. Herein, we highlight our recent discovery stereodivergent access to such useful structural motifs using Pd-catalyzed [4+2] annulation reactions vinyl benzoxazinaones and seven-membered cyclic N-sulfonyl aldimines. A wide range N-heterocycles with were obtained high efficiency stereodivergency. Importantly, the polarity solvents was found play key role switching diastereoselectivity. Furthermore, good enantioselectivities these achieved by employment commercially available Wingphos as chiral ligand.

Language: Английский

Citations

0