Iridium-Catalyzed Asymmetric Allylic Substitution Reactions

Chemical Reviews, Journal Year: 2018, Volume and Issue: 119(3), P. 1855 - 1969

Published: Dec. 24, 2018

In this review, we summarize the origin and advancements of iridium-catalyzed asymmetric allylic substitution reactions during past two decades. Since first report in 1997, Ir-catalyzed have attracted intense attention due to their exceptionally high regio- enantioselectivities. been significantly developed recent years many respects, including ligand development, mechanistic understanding, substrate scope, application synthesis complex functional molecules. an explicit outline ligands, mechanism, scope nucleophiles, applications is presented.

Language: Английский

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Catalytic Asymmetric Dearomatization by Transition-Metal Catalysis: A Method for Transformations of Aromatic Compounds

Chem, Journal Year: 2016, Volume and Issue: 1(6), P. 830 - 857

Published: Dec. 1, 2016

Language: Английский

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Progress in the Chemistry of Tetrahydroquinolines

Chemical Reviews, Journal Year: 2019, Volume and Issue: 119(8), P. 5057 - 5191

Published: April 9, 2019

Tetrahydroquinoline is one of the most important simple nitrogen heterocycles, being widespread in nature and present a broad variety pharmacologically active compounds. This Review summarizes progress achieved chemistry tetrahydroquinolines, with emphasis on their synthesis, during period from mid-2010 to early 2018.

Language: Английский

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Applications of Iridium-Catalyzed Asymmetric Allylic Substitution Reactions in Target-Oriented Synthesis

Accounts of Chemical Research, Journal Year: 2017, Volume and Issue: 50(10), P. 2539 - 2555

Published: Sept. 22, 2017

ConspectusMetal catalyzed allylic substitution is a cornerstone of organometallic and synthetic chemistry. Enantioselective versions have been developed with catalysts derived from transition metals, most notably molybdenum, nickel, ruthenium, rhodium, iridium, palladium, copper. The palladium- the iridium-catalyzed turned out to be particularly versatile in organic synthesis because very broad scope nucleophile great functional group compatibility. Assets reaction are formation branched, chiral products simple monosubstituted substrates, high degrees regio- enantioselectivity, use modular, readily available ligands. possibility carbon, nitrogen, oxygen, sulfur compounds as well fluoride nucleophiles allows wide range building blocks prepared.Our Account begins presentation fundamental schemes We will focus our discussion on reactions promoted by phosphoramidite ligands, though numerous ligands employed. subsequent section presents brief overview mechanism experimental conditions. Two emerged. In type 1 (introduced 1997), linear esters commonly used substrates under basic 2 2007), environmentally friendly branched alcohols can reacted acidic conditions; occasionally, derivatives also applied. A unique feature that highly electrophilic intermediates brought weakly activated alkenes.The text ordered according strategies followed transform desired targets, which natural or drugs. Syntheses starting an intermolecular discussed first. Some fairly complex for example, potent nitric oxide inhibitor (−)-nyasol drug (−)-protrifenbute, synthesized via less than five steps materials.Most targets cyclic compounds. Intermolecular ring closing metathesis powerful strategy their synthesis. Highlights stereodivergent syntheses Δ9-tetrahydrocannabinols (THC), wherein iridium- organocatalysis combined (dual catalysis). combination alkylation Diels–Alder was utilized synthesize ketide apiosporic acid fesoterodine (Toviaz). Sequential amination, hydroboration Suzuki–Miyaura coupling generates enones suitable conjugate addition reactions; this employed variety alkaloids, poison frog alkaloid (+)-cis-195A (pumiliotoxin C).Intramolecular substitutions offer interesting possibilities build up stereochemical complexity short routes. For diastereoselective cyclizations compounds, substrate control overruled catalyst order generate cis- trans-isomers selectively given precursor. This approach prepare piperidine pyrrolidine alkaloids. Finally, polycyclic structures, including structurally unusual indolosesquiterpenoid mycoleptodiscin A, generated diastereo- enantioselectively olefins polyene electron-rich arenes, such indoles, dearomatization reactions.

Language: Английский

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Advances in Catalytic Asymmetric Dearomatization

ACS Central Science, Journal Year: 2021, Volume and Issue: 7(3), P. 432 - 444

Published: Feb. 22, 2021

Asymmetric catalysis has been recognized as the most enabling strategy for accessing chiral molecules in enantioenriched forms. Catalytic asymmetric dearomatization is an emerging and dynamic research subject catalysis, which received considerable attention recent years. The direct transformations from readily available aromatic feedstocks to structurally diverse three-dimensional polycyclic make catalytic reactions of broad interest both organic synthesis medicinal chemistry. However, inherent difficulty disruption aromaticity demands a large energy input during process, might be incompatible with conditions generally required by catalysis. In this Outlook, we will discuss representative strategies examples various compounds try convince readers that overcoming above obstacles, could advance chemical sciences many respects.

Language: Английский

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Chiral Monophosphorus Ligands for Asymmetric Catalytic Reactions

ACS Catalysis, Journal Year: 2016, Volume and Issue: 6(8), P. 4814 - 4858

Published: June 9, 2016

Chiral monophosphorus ligands are playing an important role for the recent advances in asymmetric catalysis. This review summarizes latest progress various catalytic reactions with employment of chiral including allylic substitution, dearomative arylation, Heck reaction, cross-coupling, C–H bond functionalization, coupling π systems, addition, hydrogenation, and organocatalytic reactions. The new reactivity, selectivity, reaction mechanism enabled by these discussed.

Language: Английский

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Enantioselective γ-Alkylation of α,β-Unsaturated Malonates and Ketoesters by a Sequential Ir-Catalyzed Asymmetric Allylic Alkylation/Cope Rearrangement

Journal of the American Chemical Society, Journal Year: 2016, Volume and Issue: 138(16), P. 5234 - 5237

Published: April 7, 2016

A catalytic, enantioselective γ-alkylation of α,β-unsaturated malonates and ketoesters is reported. This strategy entails a highly regio- iridium-catalyzed α-alkylation an extended enolate, subsequent translocation chirality to the γ-position via Cope rearrangement.

Language: Английский

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Enantioselective Dearomative [3+2] Cycloaddition Reactions of Benzothiazoles

Angewandte Chemie International Edition, Journal Year: 2016, Volume and Issue: 55(45), P. 14111 - 14115

Published: Oct. 10, 2016

Abstract A highly enantioselective dearomative [3+2] cycloaddition of benzothiazole has been successfully developed. wide range benzothiazoles and cyclopropane‐1,1‐dicarboxylates are suitable substrates for this reaction. The desired hydropyrrolo[2,1‐b]thiazole compounds were obtained in excellent enantioselectivity yields (up to 97 % ee yield). With the same catalytic system, a efficient kinetic resolution 2‐substituted was also realized.

Language: Английский

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Nucleophilic Dearomatization of Activated Pyridines

Catalysts, Journal Year: 2018, Volume and Issue: 8(12), P. 632 - 632

Published: Dec. 6, 2018

Amongst nitrogen heterocycles of different ring sizes and oxidation statuses, dihydropyridines (DHP) occupy a prominent role due to their synthetic versatility occurrence in medicinally relevant compounds. One the most straightforward approaches polysubstituted DHP derivatives is provided by nucleophilic dearomatization readily assembled pyridines. In this article, we collect summarize reactions pyridines reported literature between 2010 mid-2018, complementing updating previous reviews published early 2010s dedicated various aspects pyridine chemistry. Since functionalization nitrogen, rendering (transient) pyridinium ion, usually required render nucleus sufficiently electrophilic suffer attack nucleophile, material organized according type N-functionalization. A variety species (organometallic reagents, enolates, heteroaromatics, umpoled aldehydes) can be productively engaged reactions, including catalytic asymmetric implementations, providing useful efficient platforms (enantioenriched) DHPs. Conversely, also lead ylides. These dipolar undergo cycloaddition with electron-poor dipolarophiles, affording polycyclic frameworks embedding moiety structures.

Language: Английский

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Enantio- and Diastereoselective Spiroketalization Catalyzed by Chiral Iridium Complex

Journal of the American Chemical Society, Journal Year: 2017, Volume and Issue: 139(24), P. 8082 - 8085

Published: June 9, 2017

Iridium-(P,olefin) complex-catalyzed enantio- and diastereoselective formation of substituted spiroketals from racemic, allylic carbonates is reported, which enables the installation multiple stereogenic centers in a single operation. The protocol was effective for preparation collection various ring sizes substituents, including heteroatoms with high diastereoselectivity. Furthermore, cascade reactions that couple this transformation to additional reversible processes have been achieved exert concomitant stereocontrol over centers.

Language: Английский

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