Synfacts, Год журнала: 2023, Номер 19(09), С. 0925 - 0925
Опубликована: Авг. 16, 2023
Key words remote chirality - naphthoquinone methides kinetic resolution chiral phosphoric acid
Язык: Английский
Synfacts, Год журнала: 2023, Номер 19(09), С. 0925 - 0925
Опубликована: Авг. 16, 2023
Key words remote chirality - naphthoquinone methides kinetic resolution chiral phosphoric acid
Язык: Английский
Science China Chemistry, Год журнала: 2024, Номер 67(4), С. 1175 - 1180
Опубликована: Фев. 29, 2024
Язык: Английский
Процитировано
25ACS Catalysis, Год журнала: 2024, Номер 14(12), С. 9244 - 9253
Опубликована: Июнь 3, 2024
Catalytic asymmetric dearomatization (CADA) is a powerful tool for the rapid construction of complex chiral three-dimensional cyclic molecules featuring quaternary carbon centers from readily available arenes. However, ubiquitous nonfunctionalized 1-naphthols to afford remains challenging and undeveloped. This study reports dearomative [4 + 1] spiroannulation via copper catalysis. reaction features highly chemo-, regio-, stereoselective nucleophilic addition intramolecular annulation cascade reactive π-extended copper-allenylidene, thus enabling practical synthesis range valuable spirocyclic enones bearing stereocenter with high efficiency. Furthermore, this protocol applicable phenols. Control experiments supported substitution-annulation mechanism by excluding process involving 1,3-sigmatropic shift. Preliminary biological activity studies indicated that synthesized hold significant promise as anticancer agents inducing tumor cell apoptosis.
Язык: Английский
Процитировано
13Journal of the American Chemical Society, Год журнала: 2025, Номер unknown
Опубликована: Янв. 14, 2025
Carboranyl amines are distinct from typical organic amines. Due to the electronic influence of carborane cage, they have low nucleophilicity and reluctant alkylate. Moreover, asymmetric synthesis chiral carboranes is still in its infancy. Herein we achieved first catalytic N-alkylation o-carboranyl amine, providing general access diverse secondary with high efficiency enantioselectivity under mild conditions. For time, organocatalysis was introduced chemistry. Key success use situ generated (naphtho-)quinone methides as alkylating reagents suitable acid catalysts. This protocol also applicable S-alkylation 1-SH-o-C2B10H11. Control experiments kinetic studies provided important insights into reaction mechanism, which likely involves rate-determining generation quinone methide followed by fast enantio-determining nucleophilic addition.
Язык: Английский
Процитировано
2Journal of the American Chemical Society, Год журнала: 2025, Номер unknown
Опубликована: Янв. 15, 2025
Axially chiral o-VQMs have been extensively investigated as key intermediates to approach miscellaneous structures. By sharp contrast, their structural isomers p-VQMs not previously documented. The major reason, which results in the significant delay, may ascribe inherent challenges enantioselective activation of alkynes a remote manner. Herein, we demonstrate that mechanism para-hydroxyl-substituted arylacetylenes enables stereochemical induction, resulting axially aryl-alkenes with excellent enantiopurities. A series control experiments are performed elucidate insights this asymmetric transformation and verify involvement multimolecular CPAs reaction process. These findings expected unlock new feature for VQM chemistry inspire investigation into organocatalytic stereoselectivity.
Язык: Английский
Процитировано
1Organic Letters, Год журнала: 2024, Номер 26(4), С. 845 - 849
Опубликована: Янв. 22, 2024
Visible-light-driven chemical transformation has emerged as a powerful tool for the synthesis of γ-lactams. However, during this transformation, α-bromoimides need to be pre-prepared. Herein, we report photoreodox/copper-catalyzed one-pot three-component reaction alkenes with primary amines construction In orthoquinones were generated via photocatalytic pathway, followed by attack Cu–amido complexes and intramolecular cyclization give This method represents simple synthetic route displaying broad functional group tolerance, including substrates bearing alcohols, ketones, heterocycles, esters, halides, alkynes, nitriles, ethers, etc.
Язык: Английский
Процитировано
6Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(29)
Опубликована: Май 3, 2024
The chemistry of quinone methides formed in situ has been flourishing recent years. In sharp contrast, the development and utilization biphenyl are rare. this study, we achieved a remote stereocontrolled 1,12-conjugate addition for first time. presence suitable chiral phosphoric acid, alkynyl were generated from α-[4-(4-hydroxyphenyl)phenyl]propargyl alcohols, followed by enantioselective with indole-2-carboxylates. strategy enabled alcohols to serve as efficient allenylation reagents, providing practical access broad range axially allenes bearing (1,1'-biphenyl)-4-ol unit, which previously less accessible. Combined control experiments, density functional theory calculations shed light on reaction mechanism, indicating that enantioselectivity originates nucleophilic methides. Notably, not only versatile intermediates was confirmed but also organocatalytic 1,12-addition established.
Язык: Английский
Процитировано
6Chemical Science, Год журнала: 2024, Номер 15(11), С. 3893 - 3900
Опубликована: Янв. 1, 2024
An organocatalyzed asymmetric synthesis of C sp2 –N atropisomers by formal –O amination has been established from 3-alkynyl-3-hydroxyisoindolinones and 1-methylnaphthalen-2-ols.
Язык: Английский
Процитировано
5Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(5), С. 1078 - 1083
Опубликована: Янв. 17, 2024
Abstract An organocatalytic remote stereocontrolled 1,8‐conjugated addition of in situ formed propargylic aza‐ p ‐QMs from α‐(4‐aminophenyl) alcohols and indole‐2‐carboxylates was developed, affording axially chiral tetrasubstituted allenes 62–99% yield with 52–99% ee. The synthetic strategy not only enriches the chemistry ‐quinone methides, but also provides an alternative tool for preparation allenes.
Язык: Английский
Процитировано
4Advanced Science, Год журнала: 2024, Номер 11(25)
Опубликована: Апрель 24, 2024
Abstract The efficient synthesis of chiral 2,2‐disubstituted indolin‐3‐ones is great importance due to its significant synthetic and biological applications. However, catalytic enantioselective methods for de novo such heterocycles remain scarce. Herein, a novel cyclizative rearrangement readily available anilines vicinal diketones the one‐step construction enantioenriched presented. reaction proceeds through self‐sorted [3+2] heteroannulation/regioselective dehydration/1,2‐ester shift process. Only phosphoric acid employed promote entire sequence simplify manipulation this protocol. Various common aniline derivatives are successfully applied asymmetric as 1,3‐binuclephiles first time. Remarkably, observed stereoselectivity proposed originate from an amine‐directed regio‐ ortho ‐Csp 2 ‐H addition ketones. A range transformations resulting products demonstrated well.
Язык: Английский
Процитировано
4The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(20), С. 14719 - 14727
Опубликована: Окт. 4, 2023
An efficient palladium-catalyzed enantioselective direct N-alkylation of indoles using a novel type axially chiral styrene-phosphine ligand SJTU-PHOS-1 was developed. This reaction demonstrated good functional group compatibility and wide range scope substrates in mild conditions. Moreover, the DFT calculations expounded coordination mode metal catalyst enantioselectivity control.
Язык: Английский
Процитировано
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