Organic Letters, Год журнала: 2020, Номер 22(15), С. 6122 - 6126
Опубликована: Июль 10, 2020
Easily accessible axially chiral substituted binols (95 to >99% ee) undergo an oxidative dearomatization process with the system Oxone/NaHCO3/acetone, under mild conditions, afford pentacyclic hemiacetalic cis-diols (94 ee), bearing two new stereogenic centers, through efficient axial-to-central chirality transfer.
Язык: Английский
Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(10)
Опубликована: Янв. 17, 2024
Abstract An efficient catalytic asymmetric electrophilic sulfenylation reaction for the synthesis of planar‐chiral sulfur‐containing cyclophanes has been developed first time. This was achieved by using a new Lewis base catalyst and ortho ‐trifluoromethyl‐substituted sulfenylating reagent. Using substrates with low rotational energy barrier, transformation proceeded through dynamic kinetic resolution, high barrier allowed to undergo resolution process. Meanwhile, this compatible desymmetrization process when symmetric were used. Various readily obtained in moderate excellent yields enantioselectivities (up 97 % yield 95 ee). approach used synthesize pharmaceutically relevant molecules. Density functional theory calculations showed that π‐π interactions between sulfenyl group aromatic ring substrate play crucial role enantioinduction reaction.
Язык: Английский
Процитировано
22
European Journal of Organic Chemistry, Год журнала: 2020, Номер 2020(27), С. 4087 - 4097
Опубликована: Фев. 19, 2020
The catalytic dearomatization of naphthols offers a unique platform to rapidly access structurally complex and densely functionalized molecular architectures. Thermodynamically more favorable, with respect the analogous phenol‐variant, transformation phenolic ring into corresponding naphthalenone (cited here as naphthyl dearomatization) has faced considerable amount attention over past decade constant improvements towards stereocontrol. A collection most representative recent variants involving carbon–carbon well carbon–heteroatom bond forming events are presented in this Minireview article.
Язык: Английский
Процитировано
88
Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(45), С. 19796 - 19819
Опубликована: Май 26, 2020
The last decade has witnessed a burgeoning of new methods for the enantioselective vicinal difunctionalization alkenes initiated by electrophilic sulfenyl group transfer. addition sulfenium ions to results in generation chiral, non-racemic thiiranium ions. These highly reactive intermediates are susceptible attack myriad nucleophiles stereospecific ring-opening event afford anti 1,2-sulfenofunctionalized products. practical application ion transfer been enabled advances field Lewis base catalysis. This Review will chronicle initial discovery and characterization followed determination their configurational stability challenges developing variants. Once framework reactivity established, critical analysis pioneering studies be presented. Finally, comprehensive discussion modern synthetic applications categorized around type nucleophile employed sulfenofunctionalization.
Язык: Английский
Процитировано
77
Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(23), С. 6684 - 6707
Опубликована: Янв. 1, 2022
This review systematically summarizes the recent developments for constructing sulfur compounds from electrophiles, and mechanism mainly involved thirranium ions, ylides, C–S cross coupling electrophilic substitution.
Язык: Английский
Процитировано
47
ACS Catalysis, Год журнала: 2024, Номер 14(12), С. 9254 - 9264
Опубликована: Июнь 3, 2024
Catalytic asymmetric dearomatization reactions of α-unsubstituted β-naphthols are very challenging due to the high energy barrier resulting from loss aromaticity. Herein, we describe an example enantioselective catalytic dearomative spiroannulation with yne-allylic esters. The success this reaction relied on copper-catalyzed remote strategy using esters as bis-electrophilic reagents. This transformation features mild conditions, broad functional group tolerance, and extensive substrate scope, thereby facilitating efficient construction array enantioenriched naphthalene-2-one spiroindolenine derivatives. Experimental studies density theory calculations establish pathway origin stereoselectivity.
Язык: Английский
Процитировано
12
Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(36), С. 12491 - 12496
Опубликована: Июль 11, 2019
An enantioselective sulfenylation/semipinacol rearrangement of 1,1-disubstituted and trisubstituted allylic alcohols was accomplished with a chiral Lewis base Brønsted acid as cocatalysts, generating various β-arylthio ketones bearing an all-carbon quaternary center in moderate to excellent yields enantioselectivities. These arylthio ketone products are common intermediates many applications, for example, the design new catalysts/ligands total synthesis natural products. Computational studies (DFT calculations) were carried out explain enantioselectivity role acid. Additionally, synthetic utility this method exemplified by (-)-herbertene one-pot sulfoxide sulfone.
Язык: Английский
Процитировано
63
Nature Communications, Год журнала: 2019, Номер 10(1)
Опубликована: Июль 17, 2019
Asymmetric dearomatization reactions have recently emerged as a powerful tool for the rapid build-up of molecular complexity. Chiral three-dimensional polycyclic molecules bearing contiguous stereogenic centers can be synthesized from readily available planar aromatic feedstocks. Here we report that an intermolecular asymmetric reaction α-naphthols tethered nucleophile at C4 position naphthol ring is achieved by chiral phosphoric acid. The proceeds via highly chemo- and regioselective aminative dearomatization/Michael addition sequence, affording wide array functionalized cyclic ketones in good yields (up to 93%) with excellent enantioselectivity >99% ee). catalyst loading reduced 0.1 mol%. Preliminary mechanistic investigations identify established step, while Michael rate-limiting step. A working model accounting origin stereochemistry proposed based on DFT calculations.
Язык: Английский
Процитировано
59
Nature Communications, Год журнала: 2024, Номер 15(1)
Опубликована: Ноя. 15, 2024
Inherently chiral calixarenes hold great potential for applications in recognition, sensing, and asymmetric catalysis due to their unique structures. However, special structures relatively large sizes, the catalytic synthesis of inherently is challenging with very limited examples available. Here, we present an efficient method enantioselective sulfur-containing calix[4]arenes through desymmetrizing electrophilic sulfenylation calix[4]arenes. This reaction enabled by a 1,1'-binaphthyl-2,2'-diamine-derived sulfide catalyst hexafluoroisopropanol. Various are obtained moderate excellent yields high enantioselectivities. Control experiments indicate that thermodynamically favored C-SAr product formed from kinetically N-SAr combination hexafluoroisopropanol crucially important both enantioselectivity reactivity. Due authors report
Язык: Английский
Процитировано
9
Organic Letters, Год журнала: 2018, Номер 21(1), С. 330 - 334
Опубликована: Дек. 26, 2018
The first highly stereoselective intermolecular catalytic asymmetric dearomatization (CADA) of α-naphthols through C-C formation and the allylic naphthols by chiral organocatalysis have been achieved. These new complete atom-economic reactions provide enantioriched α- β-naphthalenones bearing an all-carbon quaternary center.
Язык: Английский
Процитировано
58
The Chemical Record, Год журнала: 2020, Номер 20(11), С. 1269 - 1296
Опубликована: Сен. 15, 2020
Abstract Chiral thioethers is an important class of organosulfur molecules with extensive applications, especially in the field medicine and organic synthesis. This review discusses recent progress synthesis enantioenriched chiral hopes to be helpful for related research future. It summarized from compounds‐participating reaction types, including nucleophilic substitution, cross coupling, sulfa‐Michael addition, sulfenylation, asymmetric allylic reaction, Doyle‐Kirmse Pummerer‐type rearrangement, Smiles [2,3] Stevens Sommelet‐Hauser rearrangement.
Язык: Английский
Процитировано
47