Evolution in heterodonor P-N, P-S and P-O chiral ligands for preparing efficient catalysts for asymmetric catalysis. From design to applications DOI Creative Commons
Jèssica Margalef, Maria Biosca, Pol de la Cruz‐Sánchez

et al.

Coordination Chemistry Reviews, Journal Year: 2021, Volume and Issue: 446, P. 214120 - 214120

Published: July 19, 2021

The success of phosphine-oxazoline ligands (PHOX) inspired the progress in P-oxazoline ligand families by modifying either backbone, electronic and/or steric properties phosphine group or exchanging to a phosphinite phosphite group. In this respect, structures chiral have become more diverse and new very efficient emerged, which improved catalytic performance some asymmetric transformations, with an increased versatility, both range reactions substrates/reagents. addition, most are synthesized from easily accessible amino alcohols, maintaining short synthetic route developed for PHOX ligands. New been replacing oxazoline functionality several other N-donor groups, e.g. imidazole, thiazole, oxazole, pyridine, etc., O- S-groups. This review offers critical overview utility these successful bidentate heterodonor P-N, P-O P-S applied metal-mediated processes. We illustrate how, through proper design, can be excellent source ligands, superior many than best C2-symmetric N,N P,P-ligands reported so far.

Language: Английский

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications DOI Creative Commons
Òscar Pàmies, Jèssica Margalef, Santiago Cañellas

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(8), P. 4373 - 4505

Published: March 19, 2021

This Review compiles the evolution, mechanistic understanding, and more recent advances in enantioselective Pd-catalyzed allylic substitution decarboxylative oxidative substitutions. For each reaction, catalytic data, as well examples of their application to synthesis complex molecules, are collected. Sections which we discuss key aspects for high selectivity a comparison with other metals (with advantages disadvantages) also included. asymmetric substitution, data grouped according type nucleophile employed. Because prominent position use stabilized carbon nucleophiles heteronucleophiles, many chiral ligands have been developed. To better compare results, they presented by ligand types. reactions mainly promoted PHOX or Trost ligands, justifies organizing this section chronological order. results used.

Language: Английский

Citations

441
Asymmetric synthesis of allylic compoundsviahydrofunctionalisation and difunctionalisation of dienes, allenes, and alkynes DOI
Guanlin Li, Xiaohong Huo,

Xieyang Jiang

et al.

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(7), P. 2060 - 2118

Published: Jan. 1, 2020

This review article provides an overview of progress in asymmetric synthesis allylic compoundsviahydrofunctionalisation and difunctionalisation dienes, allenes, alkynes.

Language: Английский

Citations

316
Stereodivergent Coupling of 1,3-Dienes with Aldimine Esters Enabled by Synergistic Pd and Cu Catalysis DOI
Qinglong Zhang, Huimin Yu,

Lulu Shen

et al.

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(37), P. 14554 - 14559

Published: Sept. 3, 2019

Herein we describe the use of synergistic Pd and Cu catalysis for stereodivergent coupling reactions between 1,3-dienes aldimine esters. By using different enantiomers two metal catalysts, all four stereoisomers products, which have vicinal stereocenters, could be accessed with high diastereo- enantioselectivity. This atom-economical cross-coupling reaction has a wide substrate scope good functional group tolerance. Our work highlights power asymmetric involving Pd-hydride catalysts.

Language: Английский

Citations

245
Catalytic Enantio- and Regioselective Addition of Nucleophiles in the Intermolecular Hydrofunctionalization of 1,3-Dienes DOI
Nathan J. Adamson, Steven J. Malcolmson

ACS Catalysis, Journal Year: 2019, Volume and Issue: 10(2), P. 1060 - 1076

Published: Dec. 12, 2019

Catalytic enantioselective synthesis of small-molecule building blocks with allylic stereogenic centers is an important objective in organic synthesis, but preparing this motif wherein the adjacent olefin 1,2-disubstituted a single step tremendous challenge. Late-transition-metal-catalyzed intermolecular couplings nucleophiles and 1,3-dienes hydrofunctionalization reactions have quickly emerged as compelling approach to these related compounds. In Perspective, we illustrate how diene hydrofunctionalizations provided avenue complex, highly desirable chemical space that not readily accessed by other technologies. We also aim provide some insight into varying mechanistic pathways nuances myriad help inform future reaction catalyst design.

Language: Английский

Citations

180
Stereodivergent Synthesis of Tertiary Fluoride-Tethered Allenes via Copper and Palladium Dual Catalysis DOI

Shao‐Qian Yang,

Yifan Wang,

Wei-Cheng Zhao

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(19), P. 7285 - 7291

Published: May 10, 2021

Herein we describe a protocol for the unprecedented stereodivergent synthesis of tertiary fluoride-tethered allenes bearing stereogenic center and axis via Cu/Pd synergistic catalysis. A broad scope conjugated enynes are coupled with various α-fluoroesters in high yields diastereoselectivities generally >99% ee. In addition, four stereoisomers allene products ensure precise access to corresponding fluorinated hydrofurans novel axial-to-central chirality transfer process.

Language: Английский

Citations

167
Further Developments and Applications of Oxazoline-Containing Ligands in Asymmetric Catalysis DOI Creative Commons
Robert Connon,

Brendan Roche,

Balaji V. Rokade

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(11), P. 6373 - 6521

Published: May 21, 2021

The chiral oxazoline motif is present in many ligands that have been extensively applied a series of important metal-catalyzed enantioselective reactions. This Review aims to provide comprehensive overview the most significant applications oxazoline-containing reported literature starting from 2009 until end 2018. are classified not by reaction which their metal complexes but nature denticity, chirality, and donor atoms involved. As result, continued development ligand architectural design mono(oxazolines), bis(oxazolines), tris(oxazolines) tetra(oxazolines) variations thereof can be more easily monitored reader. In addition, key transition states selected asymmetric transformations will given illustrate features give rise high levels induction. further aid reader, we summarize majority schemes with representative examples highlight variation % yields ees for carefully substrates. should particular interest experts field also serve as useful point new researchers this area. It hoped stimulate both development/design novel transformations.

Language: Английский

Citations

135
Synergistic Pd/Amine-Catalyzed Stereodivergent Hydroalkylation of 1,3-Dienes with Aldehydes: Reaction Development, Mechanism, and Stereochemical Origins DOI
Hongfa Wang, Ruiyuan Zhang, Qinglong Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(29), P. 10948 - 10962

Published: July 15, 2021

Metal-hydride-catalyzed hydroalkylation of 1,3-dienes with enolizable carbonyl compounds is an atom- and step-economical method for preparing chiral molecules allylic stereocenters. Although high diastereo- enantioselectivities have been achieved many coupling partners, aldehydes not yet used this purpose because they are less stable than other under basic conditions the potential to rapidly epimerize at α-position. Moreover, stereodivergent reactions access complementary diastereomers vicinal stereocenters challenging. Herein, we describe a synergistic palladium/amine catalyst system that allowed us achieve first aldehydes. By choosing appropriate combination palladium amine catalysts, could obtain either syn or anti products, therefore provides highly enantioselective α,β-vicinal Density functional theory calculations revealed mechanism involving PdH formation migratory insertion into alkene, followed by C–C bond formation. The origin stereoselectivities was investigated means distortion/interaction analysis.

Language: Английский

Citations

120
Synergizing palladium with Lewis base catalysis for stereodivergent coupling of 1,3-dienes with pentafluorophenyl acetates DOI Creative Commons
Qinglong Zhang, Minghui Zhu, Weiwei Zi

et al.

Chem, Journal Year: 2022, Volume and Issue: 8(10), P. 2784 - 2796

Published: Aug. 17, 2022

Language: Английский

Citations

72
Catalytic Asymmetric Hydroalkoxylation and Formal Hydration and Hydroaminoxylation of Conjugated Dienes DOI

Shao‐Qian Yang,

Aijun Han, Yang Liu

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(7), P. 3915 - 3925

Published: Feb. 10, 2023

The straightforward construction of stereogenic centers bearing unprotected functional groups, as in nature, has been a persistent pursuit synthetic chemistry. Abundant applications free enantioenriched allyl alcohol and hydroxylamine motifs have made the asymmetric hydration hydroaminoxylation conjugated dienes from water hydroxylamine, respectively, intriguing efficient routes that have, however, unachievable thus far. A fundamental challenge is failure to realize transition-metal-catalyzed enantioselective C–O bond constructions via hydrofunctionalization dienes. Here, we perform comprehensive study toward stereoselective formal by synthesizing set new P,N-ligands identifying an aryl-derived oxime surrogate for both hydroxylamine. Asymmetric hydroalkoxylation with also elucidated. Furthermore, versatile derivatizations following provide indirect but concise hydrophenoxylation, hydrofluoroalkoxylation, hydrocarboxylation unreported Finally, ligand-to-ligand hydrogen transfer process proposed based on results preliminary mechanistic experiments.

Language: Английский

Citations

44
Enantioselective Coupling of Dienes and Phosphine Oxides DOI
Shao‐Zhen Nie,

Ryan T. Davison,

Vy M. Dong

et al.

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(48), P. 16450 - 16454

Published: Nov. 19, 2018

We report a Pd-catalyzed intermolecular hydrophosphinylation of 1,3-dienes to afford chiral allylic phosphine oxides. Commodity dienes and air stable oxides couple generate organophosphorus building blocks with high enantio- regiocontrol. This method constitutes the first asymmetric dienes.

Language: Английский

Citations

160