Synfacts, Journal Year: 2023, Volume and Issue: 19(09), P. 0925 - 0925
Published: Aug. 16, 2023
Key words remote chirality - naphthoquinone methides kinetic resolution chiral phosphoric acid
Language: Английский
Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(4), P. 1175 - 1180
Published: Feb. 29, 2024
Language: Английский
Citations
21
Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 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.
Language: Английский
Citations
2
ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(12), P. 9244 - 9253
Published: June 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.
Language: Английский
Citations
10
Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 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.
Language: Английский
Citations
1
Organic Letters, Journal Year: 2024, Volume and Issue: 26(4), P. 845 - 849
Published: Jan. 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.
Language: Английский
Citations
6
Chemical Science, Journal Year: 2024, Volume and Issue: 15(11), P. 3893 - 3900
Published: Jan. 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.
Language: Английский
Citations
5
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(29)
Published: May 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.
Language: Английский
Citations
5
Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(5), P. 1078 - 1083
Published: Jan. 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.
Language: Английский
Citations
4
Advanced Science, Journal Year: 2024, Volume and Issue: 11(25)
Published: April 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.
Language: Английский
Citations
4
Organic Letters, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 26, 2025
Organocatalytic enantioselective formal nucleophilic substitution reactions of α-(2-hydroxynaphthalen-8-yl)propargyl alcohols with 1-(1H-indol-3-yl)naphthalen-2-ols have been established for the first time. With aid a suitable chiral phosphoric acid, alkynyl 8-methylenenaphthalen-2(8H)-one was formed in situ from corresponding alcohol, followed by 1,6-conjugate additions to afford number enantioenriched (Ra,Sc)-2,3-disubstituted indoles 50-80% yields 81-93% ee and (Sa,Sc)-2,3-disubstituted 18-40% 79-96% ee. Notably, these products were characterized presence functional groups, including indole, naphthol, units, while exhibiting both axial central chirality.
Language: Английский
Citations
0