Transient Directing Groups in Metal−Organic Cooperative Catalysis DOI
Clément Jacob, Bert U. W. Maes, Gwilherm Evano

et al.

Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 27(56), P. 13899 - 13952

Published: July 19, 2021

The direct functionalization of C-H bonds is among the most fundamental chemical transformations in organic synthesis. However, when innate reactivity substrate cannot be utilized for a given single bond, this selective bond mostly relies on use directing groups that allow bringing catalyst close proximity to activated and these need installed before cleaved after transformation, which involves two additional undesired synthetic operations. These steps dramatically reduce overall impact attractiveness techniques since classical approaches based pre-functionalization are sometimes still more straightforward appealing. During past decade, different approach involving both situ installation removal group, can then often used catalytic manner, has emerged: transient group strategy. In addition its innovative character, strategy brought an unprecedented level usefulness enabled development remarkably efficient processes introduction functional onto aromatic aliphatic substrates. unlocked by will comprehensively overviewed review article.

Language: Английский

Iridium-Catalyzed Asymmetric Allylic Substitution Reactions DOI
Qiang Cheng, Hang‐Fei Tu, Chao Zheng

et al.

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

Citations

674
Palladium/Norbornene Cooperative Catalysis DOI
Jianchun Wang, Guangbin Dong

Chemical Reviews, Journal Year: 2019, Volume and Issue: 119(12), P. 7478 - 7528

Published: April 25, 2019

Palladium/norbornene cooperative catalysis has emerged as a distinct approach to construct polyfunctionalized arenes from readily available starting materials. This Review provides comprehensive overview of this field, including the early stoichiometric investigations, catalytic reaction developments, well applications in syntheses bioactive compounds and polymers. The section reactions is divided into two parts according initiation mode: Pd(0)-initiated Pd(II)-initiated reactions.

Language: Английский

Citations

442
Iridium-Catalyzed Asymmetric Synthesis of Functionally Rich Molecules Enabled by (Phosphoramidite,Olefin) Ligands DOI
Simon L. Rössler,

David A. Petrone,

Erick M. Carreira

et al.

Accounts of Chemical Research, Journal Year: 2019, Volume and Issue: 52(9), P. 2657 - 2672

Published: June 19, 2019

ConspectusThe catalytic, asymmetric synthesis of complex molecules has been a core focus our research program for some time because developments in the area can have an immediate impact on identification novel strategies value-added molecules. In concert with this central interest, we emphasized design ligand scaffolds as tactic to discover and develop chemistry overcome well-recognized synthetic challenges. Based group's work chiral pool-derived diolefin ligands, designed implemented class hybrid (phosphoramidite,olefin) which combines properties both phosphoramidite olefin motifs impact, fine-tune, even override inherent reactivity metal center. Specifically, utilized these unique modifying ligands address several recognized limitations field iridium-catalyzed, allylic substitution. The methods documented typically employ branched, unprotected alcohols substrates obviate need rigorous exclusion air moisture.Following Takeuchi's seminal report demonstrating high aptitude Ir(I)-phosphite catalysts branch-selective substitution, concerted efforts from numerous laboratories led broadening utility reaction class. first section Account outlines process leading discovery unprecedented its validation iridium-catalyzed amination alcohols. This continues involving heteroatom-based nucleophiles within inter- intramolecular etherification, thioetherification spiroketalization processes. second highlights use readily available carbon possessing sp, sp2, sp3 hybridization series enantioselective carbon–carbon bond-forming reactions. We describe how alkylzinc, allylsilane, classes organotrifluoroborate be coupled enantioselectively enable construction key including 1,5-dienes, 1,4-dienes, 1,4-enynes. Since electronic steric renders (η3-allyl)-Ir(III) intermediate highly electrophilic, weak such alkyl olefins used. also show that more nucleophilic alkene enamines situ generated ketene acetals smoothly participate substitution reactions yield valuable piperidines γ,δ-unsaturated esters, respectively.The concept stereodivergent dual catalysis, synergistically amine catalysis iridium furnish α-allylated aldehydes containing two independently controllable stereocenters is then discussed. enabled independent, stereoselective all four possible product stereoisomers single set starting materials, was highlighted Δ9-tetrahydrocannabinol. concludes overview organometallic mechanistic studies regarding relevant intermediates catalytic cycle These allowed us better understand origin characteristics exhibited by catalyst comparison related systems.

Language: Английский

Citations

327
Catalytic asymmetric dearomatization (CADA) reaction-enabled total synthesis of indole-based natural products DOI
Chao Zheng, Shu‐Li You

Natural Product Reports, Journal Year: 2019, Volume and Issue: 36(11), P. 1589 - 1605

Published: Jan. 1, 2019

The recent enantioselective total syntheses of natural products enabled by catalytic asymmetric dearomatization reactions indole derivatives are presented.

Language: Английский

Citations

310
Applications of Iridium-Catalyzed Asymmetric Allylic Substitution Reactions in Target-Oriented Synthesis DOI
Jian‐Ping Qu,

Günter Helmchen

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

Citations

307
Recent progress in transition-metal-catalyzed enantioselective indole functionalizations DOI
Jing-Biao Chen, Yi‐Xia Jia

Organic & Biomolecular Chemistry, Journal Year: 2017, Volume and Issue: 15(17), P. 3550 - 3567

Published: Jan. 1, 2017

Numerous efficient synthetic methods for enantioselective indole functionalizations have emerged in recent years. This review summarizes the major achievements transition-metal-catalyzed functionalization reactions since 2010 and focuses on C-C bond formation processes, including alkylations, arylations, cycloaddition reactions, other reactions. It intends to give a compendious overview of significant progress achieved this area.

Language: Английский

Citations

256
Strategic evolution in transition metal-catalyzed directed C–H bond activation and future directions DOI
Supriya Rej, Amrita Das, Naoto Chatani

et al.

Coordination Chemistry Reviews, Journal Year: 2020, Volume and Issue: 431, P. 213683 - 213683

Published: Dec. 9, 2020

Language: Английский

Citations

226
Palladium(II)‐Initiated Catellani‐Type Reactions DOI
Hong‐Gang Cheng, Shuqing Chen, Ruimin Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 58(18), P. 5832 - 5844

Published: Dec. 27, 2018

Abstract The Catellani reaction is known as a powerful strategy for the expeditious synthesis of highly substituted arenes and benzo‐fused rings, which are usually difficult to access through traditional cross‐coupling strategies. It utilizes synergistic interplay palladium norbornene catalysis facilitate sequential ortho C−H functionalization ipso termination aryl halides in single operation. In classical Catellani‐type reactions, mainly used substrates, Pd 0 catalyst required initiate reaction. Nevertheless, recent advances showcase that reactions can also be initiated by II with different starting materials instead via mechanisms under conditions. This emerging concept /norbornene cooperative has significantly advanced thus enabling future developments this field. Minireview, ‐initiated their application bioactive molecules summarized.

Language: Английский

Citations

187
Enantioselective formation of quaternary carbon stereocenters in natural product synthesis: a recent update DOI
Chengxi Li,

Sherif S. Ragab,

Guodu Liu

et al.

Natural Product Reports, Journal Year: 2019, Volume and Issue: 37(2), P. 276 - 292

Published: Sept. 13, 2019

The enantioselective formation of quaternary carbon stereocenters in complex natural product synthesis the latest six years is reviewed, with particular emphasis on analysis stereochemical model each transformation.

Language: Английский

Citations

177
Cascade asymmetric dearomative cyclization reactions via transition-metal-catalysis DOI
Yang‐Zi Liu, Hao Song, Chao Zheng

et al.

Nature Synthesis, Journal Year: 2022, Volume and Issue: 1(3), P. 203 - 216

Published: March 14, 2022

Language: Английский

Citations

78