Enantioselective and Enantiospecific Transition-Metal-Catalyzed Cross-Coupling Reactions of Organometallic Reagents To Construct C–C Bonds

Chemical Reviews, Год журнала: 2015, Номер 115(17), С. 9587 - 9652

Опубликована: Авг. 13, 2015

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTEnantioselective and Enantiospecific Transition-Metal-Catalyzed Cross-Coupling Reactions of Organometallic Reagents To Construct C–C BondsAlan H. Cherney, Nathaniel T. Kadunce, Sarah E. Reisman*View Author Information The Warren Katharine Schlinger Laboratory for Chemistry Chemical Engineering, Division California Institute Technology, Pasadena, 91125, United States*E-mail: [email protected]Cite this: Chem. Rev. 2015, 115, 17, 9587–9652Publication Date (Web):August 13, 2015Publication History Received17 March 2015Published online13 August inissue 9 September 2015https://doi.org/10.1021/acs.chemrev.5b00162Copyright © 2015 American SocietyRIGHTS & PERMISSIONSACS AuthorChoiceArticle Views40232Altmetric-Citations603LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum full text article downloads since November 2008 (both PDF HTML) across all institutions individuals. These metrics regularly updated to reflect usage leading up last few days.Citations number other articles citing this article, calculated by Crossref daily. Find more information about citation counts.The Altmetric Attention Score is a quantitative measure attention that research has received online. Clicking on donut icon will load page at altmetric.com with additional details score social media presence given article. how calculated. Share Add toView InAdd Full Text ReferenceAdd Description ExportRISCitationCitation abstractCitation referencesMore Options onFacebookTwitterWechatLinked InReddit (12 MB) Get e-AlertsSUBJECTS:Cross coupling reaction,Electrophiles,Ligands,Reagents,Substitution reactions e-Alerts

Язык: Английский

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Transition-Metal-Catalyzed Asymmetric Allylic Dearomatization Reactions

Accounts of Chemical Research, Год журнала: 2014, Номер 47(8), С. 2558 - 2573

Опубликована: Июнь 18, 2014

ConspectusDearomatization reactions serve as powerful methods for the synthesis of highly functionalized, three-dimensional structures starting with simple planar aromatic compounds. Among processes this type, catalytic asymmetric dearomatization (CADA) are attractive owing to large number compounds that readily available and fact they enable direct access enantiopure polycycles spirocycles, which frequently key structural motifs in biologically active natural products pharmaceuticals. However, a consequence their high stabilities, arenes only difficultly participate take place levels enantioselectivity.Transition-metal-catalyzed allylic substitution have been demonstrated be enantioselective formation C–C C–X (X = O, N, S, etc.) bonds. scope these has explored mainly using soft carbon nucleophiles, some hard nucleophiles such enolates preformed organometallic reagents, heteroatom nucleophiles. Readily accessible rarely used directly reactions.In Account, we present results studies conducted aimed at development transition-metal-catalyzed reactions. By utilizing general process, devised indoles, pyrroles, phenols, naphthols, pyridines, pyrazines, produce various functionalized bearing all-carbon quaternary stereogenic centers straightforward manner. In mechanistic investigations found five-membered spiroindolenines intermediates, undergo stereospecific migration form corresponding tetrahydro-1H-carbazoles upon treatment amount TsOH. It is worth noting no notable loss enantiomeric excess spiroindolenine derivatives takes during rearrangement process intervention "three-center–two-electron"-type transition state, proposal gained support from DFT calculations. Equally intriguing, tuning electronic nature tethers, pyrroles or indoles unprecedented Ir Ru catalyzed intramolecular alkylation promoted dearomatization/migration The operation novel reaction pathway provides additional information leading greater understanding functionalizations indoles. combined effort provide not efficient enantioenriched fused spiro but also strategies field catalysis.

Язык: Английский

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Catalytic Enantioselective Construction of Quaternary Stereocenters: Assembly of Key Building Blocks for the Synthesis of Biologically Active Molecules

Accounts of Chemical Research, Год журнала: 2015, Номер 48(3), С. 740 - 751

Опубликована: Фев. 25, 2015

The ever-present demand for drugs with better efficacy and fewer side effects continually motivates scientists to explore the vast chemical space. Traditionally, medicinal chemists have focused much attention on achiral or so-called "flat" molecules. More recently, has shifted toward molecules stereogenic centers since their three-dimensional structures represent a larger fraction of space number superior properties compared flat aromatic compounds. Quaternary stereocenters, in particular, add greatly three-dimensionality novelty molecule. Nevertheless, synthetic challenges building quaternary stereocenters largely prevented implementation drug discovery. lack effective broadly general methods enantioselective formation simple molecular scaffolds prompted us investigate new chemistry develop innovative tools solutions. In this Account, we describe three approaches constructing stereocenters: nucleophilic substitution 3-halooxindoles, conjugate addition boronic acids cyclic enones, allylic alkylation enolates. first approach, malonic ester nucleophiles attack electrophilic mediated by copper(II)-bisoxazoline catalyst. A variety oxindoles containing benzylic stereocenter can be accessed through method. However, it is only applicable specialized 3,3-disubstituted oxindole system. To access more context, turned our carbon α,β-unsaturated carbonyl acceptors. We discovered that presence catalytic palladium-pyridinooxazoline complex, arylboronic smoothly β-substituted enones furnish ketones β-benzylic high yields enantioselectivities. reaction compatible wide range acids, β-substituents, ring sizes. Aside from challenging motif not adjacent an group. Such but are difficult form asymmetric catalysis. address greater challenge, motivated reward, entered field palladium-catalyzed prochiral enolate about decade ago. On basis Tsuji's work, which solved issue positional selectivity unsymmetrical ketones, phosphinooxazoline ligand effectively rendered enantioselective. Extensive investigations then revealed exhibits broad scope accepts substrate classes, each its unique advantage applications. diverse array compounds bearing α-quaternary obtained excellent enantioselectivities, possibilities yet explored. As alternative palladium catalysis, also studied iridium-catalyzed alkylations generate vicinal tertiary single transformation. Overall, these provide small molecule blocks stereocenter, applied various scaffolds, tolerate functional groups. envision reported Account will increasingly useful discovery design.

Язык: Английский

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Iridium-Catalyzed Asymmetric Allylic Substitution Reactions

Chemical Reviews, Год журнала: 2018, Номер 119(3), С. 1855 - 1969

Опубликована: Дек. 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.

Язык: Английский

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Combinations of Aminocatalysts and Metal Catalysts: A Powerful Cooperative Approach in Selective Organic Synthesis

Chemical Reviews, Год журнала: 2016, Номер 116(22), С. 13512 - 13570

Опубликована: Окт. 10, 2016

The cooperation and interplay between organic metal catalyst systems is of utmost importance in nature chemical synthesis. Here innovative selective cooperative can be designed by combining two catalysts that complement rather than inhibit one another. This refined strategy permit transformations unmanageable either the alone. review summarizes innovations developments synthesis have used dual catalysis simple aminocatalysts with catalysts. Considerable efforts been devoted to this fruitful field. emerging area employs different activation modes amine as a platform address challenging reactions. Here, aminocatalysis (e.g., enamine catalysis, iminium single occupied molecular orbital (SOMO) photoredox catalysis) employed activate unreactive carbonyl substrates. transition complements activating variety substrates through range interactions electrophilic π-allyl complex formation, Lewis acid activation, allenylidene C-H etc.), thereby novel concepts within are created. inclusion heterogeneous strategies allows for "green" chemistry development, recyclability, more eco-friendly valuable compounds.

Язык: Английский

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Stereodivergent α-Allylation of Linear Aldehydes with Dual Iridium and Amine Catalysis

Journal of the American Chemical Society, Год журнала: 2014, Номер 136(8), С. 3020 - 3023

Опубликована: Фев. 9, 2014

We describe the fully stereodivergent, dual catalytic α-allylation of linear aldehydes. The reaction proceeds via direct iridium-catalyzed substitution racemic allylic alcohols with enamines generated in situ. use an Ir(P,olefin) complex and a diarylsilyl prolinol ether as catalysts presence dimethylhydrogen phosphate promoter proved to be crucial for achieving high enantio- diastereoselectivity (>99% ee, up >20:1 dr). utility method is demonstrated concise enantioselective synthesis antidepressant (-)-paroxetine.

Язык: Английский

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Ir/Cu Dual Catalysis: Enantio- and Diastereodivergent Access to α,α-Disubstituted α-Amino Acids Bearing Vicinal Stereocenters

Journal of the American Chemical Society, Год журнала: 2018, Номер 140(6), С. 2080 - 2084

Опубликована: Янв. 30, 2018

We describe a fully stereodivergent synthesis of range α,α-disubstituted α-amino acids via an Ir/Cu-catalyzed α-allylation readily available imine esters. The introduction Cu-Phox complex-activated ester into the chiral iridium-catalyzed allylic allylation process is crucial for its high reactivity and excellent enantio- diastereoselectivity (up to >99% ee >20:1 dr). Importantly, two catalysts allow full control over configuration stereocenters, affording all stereoisomers desired products. utility this methodology was demonstrated by synthesizing dipeptides analogues bioactive molecules in manner.

Язык: Английский

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

Accounts of Chemical Research, Год журнала: 2017, Номер 50(10), С. 2539 - 2555

Опубликована: Сен. 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.

Язык: Английский

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Stereodivergent Allylic Substitutions with Aryl Acetic Acid Esters by Synergistic Iridium and Lewis Base Catalysis

Journal of the American Chemical Society, Год журнала: 2016, Номер 139(1), С. 87 - 90

Опубликована: Дек. 17, 2016

The preparation of all possible stereoisomers a given chiral molecule bearing multiple stereocenters by simple and unified method is significant challenge in asymmetric catalysis. We report stereodivergent allylic substitutions with aryl acetic acid esters catalyzed synergistically metallacyclic iridium complex benzotetramisole. Through permutations the enantiomers two catalysts, four products adjacent are accessible high diastereoselectivity enantioselectivity. resulting activated ester can be converted readily to enantioenriched amides, unactivated esters, carboxylic acids one-pot manner.

Язык: Английский

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Iridium-Catalyzed Enantioselective Allylic Vinylation

Journal of the American Chemical Society, Год журнала: 2012, Номер 135(3), С. 994 - 997

Опубликована: Дек. 21, 2012

The first example of Ir-catalyzed asymmetric substitution reaction with vinyl trifluoroborates is described. direct between branched, racemic allylic alcohols and potassium alkenyltrifluoroborates proceeded high site selectivity excellent enantioselectivity (up to 99%) mediated by an Ir-(P,olefin) complex. This method allows rapid access various 1,4-dienes or trienes including the biologically active natural products (-)-nyasol (-)-hinokiresinol.

Язык: Английский

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