Gold(I)/Chiral <i>N</i>,<i>N′</i>‐Dioxide–Nickel(II) Relay Catalysis for Asymmetric Tandem Intermolecular Hydroalkoxylation/Claisen Rearrangement

Li, Jun; Lin, Lili; Hu, Bowen; Zhou, Pengfei; Huang, Tianyu; Liu, Xiaohua; Feng, Xiaoming

doi:10.1002/anie.201611214

Cited by 97 publications

(18 citation statements)

References 79 publications

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“…33 Despite these advances and many other approaches for the assembly of complex molecules with an alkynyl species, [34][35][36][37] the direct catalytic asymmetric propargyloxylation reaction has not yet been reported. Although intensive efforts have been devoted to the asymmetric oxyalkylation, [38][39][40] the analogous highly enantioselective version with propargyl alcohol as a readily available reagent is rather limited and still represents a formidable challenge due to the linear-type structural characteristic of this species. Thus, the design and development of an appropriate catalytic system, or conditions, for asymmetric propargyloxylation with commercially available propargyl alcohols as starting materials is a critical objective in catalytic and synthetic chemistry.…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Three-Component Propargyloxylation for Direct Assembly of Polyfunctionalized Chiral Succinate Derivatives

Liu

Zhou

et al. 2021

CCS Chem

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An enantioselective three-component propargyloxylation reaction of propargyl alcohols, pyridotriazoles, and imines has been realized by cooperative catalysis with dirhodium complex and chiral phosphoric acid under mild conditions. This is the first example of a catalytic asymmetric three-component propargyloxylation reaction, which provides practical access to chiral polyfunctionalized succinate derivatives with adjacent quaternary and tertiary stereocenters in good to high yields with excellent enantioselectivity. In addition to the alkyne motif, pyridyl, alkoxy, amino, and alkenyl species are all tolerated under the reaction conditions. Notably, the utility of the current method is demonstrated by catalytic cyclization of the product alkyne into a variety of heterocyclic structures without loss of enantiomeric purity.

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Section: Introductionmentioning

confidence: 99%

Asymmetric Three-Component Propargyloxylation for Direct Assembly of Polyfunctionalized Chiral Succinate Derivatives

Liu

Zhou

et al. 2021

CCS Chem

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“…[ 46 ] Similarly, asymmetric tandem intermolecular hydroalkoxylation/Claisen rearrangement was realized through Au(I)/ N , N '‐ dioxide‐Ni(II) relay catalysis (Scheme 15b). [ 47 ] The combination of Grubbs 2 nd generation catalysts and N , N '‐dioxide‐Ni(II) complex achieved the enantionselective synthesis of 6‐aryl‐spiro‐[5,6]‐ bicyclic derivatives via olefin metathesis/Diels‐Alder reaction (Scheme 15c). [ 48 ]…”

Section: Representative Applicationsmentioning

confidence: 99%

Feng Ligand: Privileged Chiral Ligand in Asymmetric Catalysis

Wang

2021

Chin. J. Chem.

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Feng ligand | N,N'-Dioxide | O ligands | Asymmetric catalysis | Lewis acids Catalysts and ligands possessing the great ability to tolerate over a wide range of mechanistically unrelated reactions are remarked as "privileged", which are rather scarce but extremely meaningful in asymmetric catalysis. Feng and co-workers have developed a library of conformationally flexible, C 2-symmetric N,N'-dioxide amide compounds with original design and featured structure (named as Feng ligand now). They were initially reported as chiral organocatalysts in 2005 and have been further developed as a new class of privileged chiral ligands since 2006. Tremendous success, including versatile coordination chemistry with plenty of metal sources (main-group metals, transition metals, and rare-earth metals), a truly broad scope of asymmetric reactions (more than 50 types), diverse areas of catalysis (organocatalysis, Lewis-acid catalysis, bimetallic relay catalysis, and photocatalysis), numerous synthetic applications of bioactive compounds, has been achieved using Feng N,N'-dioxide. Besides, they demonstrate that chiral ligands with conformationally flexible property can offer excellent chiral environment as well, which challenges the conventional idea preferring rigid structures in the design of chiral ligands. Herein, we briefly introduced the discovery of Feng ligand and the millstones during the development. We also covered the successful applications of Feng ligand by other scientists as well as novel chiral ligands inspired by them. Contents 1. Introduction 969 2. Initial Discovery 970 3. Representative Applications 971 3.1. Classical asymmetric reactions 971 3.2. Novel asymmetric reactions 975 4. Studies by Other Groups 977 4.1. Reactions using Feng ligand 977 4.2. Novel chiral ligands inspired by Feng ligand 980 5. Conclusions 980

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“…In another context, Feng and Liu described in 2017 an enantioselective gold‐ and nickel‐catalyzed domino hydroalkoxylation/Claisen rearrangement reaction of alkynyl esters 128 with allylic alcohols 30 / 38 / 129 to give the corresponding chiral acyclic α‐allyl β‐keto esters 130 . The process involved a hydroalkoxylation reaction catalyzed by 1 mol% of π‐acidic gold(I) complex IPrAuCl followed by a Claisen rearrangement catalyzed by a chiral Lewis acidic nickel(II) complex in situ generated from 2.5 mol% of Ni(ClO 4 ) 2 and the same quantity of chiral N,N′ ‐dioxide ligand 131 .…”

Section: Enantioselective Tandem Reactions Catalyzed By Two Metalsmentioning

confidence: 99%

Recent Developments in Enantioselective Multicatalyzed Tandem Reactions

Pellissier

2020

Adv Synth Catal

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This review presents an update on the emerging field of enantioselective multicatalyzed tandem reactions published since the beginning of 2015. It illustrates how much the combination of different types of catalyst allows unprecedented enantioselective one‐pot reactions of many types to be achieved, allowing a direct access to a variety of very complex chiral molecules. Abbreviations: acac: acetylacetonate; Ar: aryl; Bn: benzyl; Boc: tert‐butoxycarbonyl; BPE: 1,2‐bis(2‐pyridyl)ethane; Bz: benzoyl; CAPT: chiral anion phase‐transfer; Cbz: benzyloxycarbonyl; cod: cyclooctadiene; Cy: cyclohexyl; dba: (E,E)‐dibenzylideneacetone; DBU: 1,8‐diazabicyclo[5.4.0]undec‐7‐ene; DCE: dichloroethane; de: diastereomeric excess; DIPEA: diisopropylethylamine; dme: 1,2‐dimethoxyethane; DPG: 1,3‐diphenylguanidine; dppe: 1,2‐bis(diphenylphosphino)ethane; ee: enantiomeric excess; EWG: electron‐withdrawing group; Hept: heptyl; Hex: hexyl; L: ligand; MTBE: methyl tert‐butyl ether; MOM: methoxymethyl; MS: molecular sieves; Naph: naphthyl; NHC: N‐heterocyclic carbene; Pent: pentyl; Phth: phthaloyl; pin: pinacolato; Pybox: 2,6‐bis(2‐oxazolyl)pyridine; r.t.: room temperature; TEMPO: 2,2,6,6‐tetramethylpiperidine 1‐oxyl; Tf: trifluoromethanesulfonyl; THF: tetrahydrofuran; TMP: 2,2,6,6‐tetramethylpiperidine; TMS: trimethylsilyl; Tol: tolyl; triphos: bis(diphenylphosphinoethyl)phenylphosphine; Ts: 4‐toluenesulfonyl (tosyl).

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Gold(I)/Chiral N,N′‐Dioxide–Nickel(II) Relay Catalysis for Asymmetric Tandem Intermolecular Hydroalkoxylation/Claisen Rearrangement

Cited by 97 publications

References 79 publications

Asymmetric Three-Component Propargyloxylation for Direct Assembly of Polyfunctionalized Chiral Succinate Derivatives

Asymmetric Three-Component Propargyloxylation for Direct Assembly of Polyfunctionalized Chiral Succinate Derivatives

Feng Ligand: Privileged Chiral Ligand in Asymmetric Catalysis

Recent Developments in Enantioselective Multicatalyzed Tandem Reactions

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