This review summarizes the progresses in organocatalytic asymmetric dearomatization reactions of indole derivatives and their applications total synthesis natural products, gives some insights into challenging issues this research field.

Atroposelective synthesis of axially chiral molecules has attracted substantial attention from chemists because the importance such molecules. However, catalytic asymmetric styrenes or vinyl arenes is underdeveloped and challenging due to low rotational barrier weak configurational stability Therefore, development powerful strategies for atroposelective great importance. In this work, we have accomplished first access oxindole-based by strategy kinetic resolution, offered two kinds styrene...

Catalytic asymmetric construction of chiral indole-fused rings has become an important issue in the chemical community because significance such scaffolds. In this work, we have accomplished first catalytic (4+2) and (4+3) cycloadditions 2,3-indolyldimethanols by using indoles 2-naphthols as suitable reaction partners under catalysis phosphoric acids, constructing enantioenriched six-membered seven-membered high yields with excellent enantioselectivities. addition, approach is used to...

The first catalytic asymmetric isatin-involved Povarov reaction has been established. This method provides an unprecedented approach to access the enantioenriched spiro[indolin-3,2'-quinoline] scaffold with concomitant creation of two quaternary stereogenic centers in high yields and excellent stereoselectivities (all >99:1 dr's, up 97% ee).

An organocatalytic asymmetric formal [3+2] cycloaddition of isatin-derived 3-indolylmethanol with 3-methyl-2-vinylindole has been established, leading to highly stereoselective construction a spiro[cyclopenta[b]indole-1,3′-oxindole] scaffold the concomitant creation three contiguous stereogenic centers (72–99% yield, all >95 : 5 dr, 90–98% ee), one which is an all-carbon quaternary center.

A copper-catalyzed condensation reaction of oxime acetates and α,β-unsaturated ketimines to give pyridine derivatives is reported. The features mild conditions, high functional-group compatibility, regioselectivity with respect unsymmetrical acetates, thus allowing the preparation a wide range polysubstituted pyridines, many which are not readily accessible by conventional methods.

Abstract The regio‐ and enantioselective (3+3) cycloaddition of nitrones with 2‐indolylmethanols was accomplished by the cooperative catalysis hexafluoroisopropanol (HFIP) chiral phosphoric acid (CPA). Using this approach, a series indole‐fused six‐membered heterocycles were synthesized in high yields (up to 98 %), excellent enantioselectivities 96 % ee ) exclusive regiospecificity. This approach enabled not only first organocatalytic asymmetric but also C3‐nucleophilic 2‐indolylmethanols....

Main observation and conclusion Atroposelective construction of axially chiral alkene‐heteroaryl scaffolds is highly desired but challenging. In this work, we established an atroposelective alkene‐indole via the strategy catalytic enantioselective addition reaction 3‐alkynyl‐2‐indolylmethanols with bulky nucleophiles. strategy, α‐amido sulfones were used as competent nucleophiles phosphoric acid (CPA) acted suitable catalyst for reaction. By a new class acyclic alkene‐indoles was synthesized...

Summary of main observation and conclusion An atroposelective synthesis a new class 3,3’‐bisindoles bearing axial central chirality has been established via catalytic asymmetric addition reactions using isatin‐derived imines as electrophiles (23 examples, up to 80% yield, > 95 : 5 dr, 98 2 er). This approach takes advantage chiral phosphoric acid‐catalyzed dynamic kinetic resolution 2‐substituted nucleophilic such substrates with imines. In this approach, acted competent due their high...

The catalytic asymmetric construction of axially chiral indole-based frameworks is an important area research due to the unique characteristics such frameworks. Nevertheless, in this still its infancy and has some challenges, as designing constructing new classes scaffolds developing their applications catalysts, ligands, etc. To overcome these we present herein design atroposelective synthesis aryl-pyrroloindoles a class via strategy organocatalytic (2 + 3) cyclization between 3-arylindoles...

Comprehensive Summary A new class of m ‐hydroxybenzyl alcohols has been designed as competent three‐carbon building blocks and achieved their application in 2‐indolylmethanol‐involved regioselective (3 + 3) cycloadditions under the catalysis Brønsted acids. By this appoach, a series indole‐fused six‐membered cycloadducts have synthesized overall good yields (up to 98%) with excellent regioselectivity (all >95: 5 rr), thus affording powerful method for construction rings. Moreover,...

Abstract In the chemistry community, catalytic asymmetric synthesis of furan‐based compounds bearing both axial and central chirality has proven to be a significant but challenging issue owing importance difficulty in constructing such frameworks. this work, we have realized first five‐five‐membered via organocatalytic (2+4) annulation achiral furan‐indoles with 2,3‐indolyldimethanols uncommon regioselectivity. By strategy, furan‐indole were synthesized high yields excellent regio‐,...

An efficient and practical thiocarbonyl surrogate via combination of sulfur chloroform has been developed. A variety thiocarbamides oxazolidinethiones have established, including chiral thiourea catalysts oxazolidinethione auxiliaries with high selectivity. Meanwhile, pesticides Diafenthiuron (an acaricide), ANTU (a rodenticide), Chloromethiuron insecticide) were practically synthesized through this method in gram scale. Dicholorocarbene, as the key intermediate, was further confirmed a...

The catalytic asymmetric aza-ene reactions of 3-indolylmethanols with cyclic enaminones and the highly enantioselective utilizing components have been established, which directly assemble isatin-derived dimedone-derived into C3-functionalized chiral indoles one all-carbon quaternary stereogenic center in high yields excellent enantioselectivities (up to 99% yield, up 95:5 er).

In recent years, it has become an urgent task to design new types of indole-based platform molecules for Nazarov-type cyclizations and develop organocatalytic synthesizing indole derivatives. To fulfill this task, in work, by changing the alkynyl terminal substituent from t-Bu aryl group, reactivity 3-alkynyl-2-indolylmethanols is modulated serve as competent substrates Brønsted acid-catalyzed cyclization. Based on reactivity, first cyclization aryl-substituted with 2-naphthols accomplished,...

Abstract The first catalytic asymmetric five‐component tandem reactions of β‐keto esters, aromatic aldehydes and anilines have been established in the presence a chiral phosphoric acid, affording densely functionalized tetrahydropyridines with concomitant generation five σ bonds two stereogenic centers high diastereo‐ enantioselectivities (up to >99:1 dr , 95:5 er ). In addition, isolation preparation diene species as key intermediate reaction has successfully realized, leading formation...

The construction of a spiro-oxindole-based 2,5-dihydropyrrole scaffold with potential bioactivity has been established via an efficient three-component reaction isatin, amino-ester and alkyne. This protocol represents the first 1,3-dipolar cycloaddition electron-deficient alkynes isatin-derived azomethine ylides, providing easy access to 2,5-dihydropyrroles structural diversity in high yields (up 99%). In addition, bioscreen these new spiro-dihydropyrroles led finding sixteen compounds...