Recent advances in copper-catalyzed propargylic substitution

Zhang, Deyang; Hu, Xiang‐Ping

doi:10.1016/j.tetlet.2014.11.112

Cited by 240 publications

(59 citation statements)

References 82 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[1][2][3][4] Very recently,wedisclosed the first copper-catalyzed asymmetric formal [3+ +2] cycloaddition of propargylic esters as C 2 synthons with C,O-bis(nucleophile)s, b-ketoesters,b yasequential propargylic alkylation/intramolecular hydroalkoxylation process. [5] However,t he use of other bis(nucleophile)s for this cycloaddition remains unexplored.…”

mentioning

confidence: 99%

“…Catalytic asymmetric propargylic transformations of terminal propargylic compounds with nucleophiles,t ransformations featuring metal allenylidene complexes as the key intermediates,h ave attracted much attention because of its high potential in the enantioselective formation of CÀCa nd C-heteroatom bonds. [1][2][3][4] Very recently,wedisclosed the first copper-catalyzed asymmetric formal [3+ +2] cycloaddition of propargylic esters as C 2 synthons with C,O-bis(nucleophile)s, b-ketoesters,b yasequential propargylic alkylation/intramolecular hydroalkoxylation process. [5] However,t he use of other bis(nucleophile)s for this cycloaddition remains unexplored.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Desilylation‐Activated Propargylic Transformation: Enantioselective Copper‐Catalyzed [3+2] Cycloaddition of Propargylic Esters with β‐Naphthol or Phenol Derivatives

Shao,

Wang,

Zhang

et al. 2016

Angew Chem Int Ed

Self Cite

117

View full text Add to dashboard Cite

A copper-catalyzed asymmetric [3+2] cycloaddition of 3-trimethylsilylpropargylic esters with either β-naphthols or electron-rich phenols has been realized and proceeds by a desilylation-activated process. Under the catalysis of Cu(OAc)2⋅H2O in combination with a structurally optimized ketimine P,N,N-ligand, a wide range of optically active 1,2-dihydronaphtho[2,1-b]furans or 2,3-dihydrobenzofurans were obtained in good yields and with high enantioselectivities (up to 96 % ee). This represents the first desilylation-activated catalytic asymmetric propargylic transformation.

show abstract

mentioning

confidence: 99%

mentioning

confidence: 99%

Desilylation‐Activated Propargylic Transformation: Enantioselective Copper‐Catalyzed [3+2] Cycloaddition of Propargylic Esters with β‐Naphthol or Phenol Derivatives

Shao,

Wang,

Zhang

et al. 2016

Angew Chem Int Ed

Self Cite

117

View full text Add to dashboard Cite

show abstract

“…[4,5] While synthetically useful, this method generates propargyl amine with as ingle stereocenter through the alkynyl addition step. [6] Thes econd strategy,n amely propargylic substitution, [7] delivers chiral propargyl amines through catalytic substitution of propargylic electrophile with an amine. [8] Similarly,o nly one stereocenter is formed in the propargylic amine product.…”

Section: Introductionmentioning

confidence: 99%

Highly Enantioselective Synthesis of Propargyl Amide with Vicinal Stereocenters through Ir‐Catalyzed Hydroalkynylation

Zhang

2020

Angewandte Chemie

View full text Add to dashboard Cite

Chiral propargyl amines are valuable synthetic intermediates for the preparation of biologically active compounds and functionalizedamines.Catalytic methods to access propargyl amines containing vicinal stereocenters with high diastereoselectivity are particularly rare.W er eport an unprecedented strategy for the synthesis of enantioenriched propargyl amines with two stereogenic centres.Aniridium complex, ligated by ap hosphoramidite ligand, catalyzest he hydroalkynylation of b,b-disubstituted enamides to affordpropargyl amides in ah ighly regio-, diastereo-, and enantioselective fashion. Stereodivergent synthesis of all four possible stereoisomers was achieved using this strategy. Scheme 1. Strategies for the preparation of propargyl amines.

show abstract

“…When considering the use of fluoride anions in propargylic substitution reactions, [20] our attention was drawn to as tudy by Murahashi and co-workers on the copper(I)-catalyzed amination of propargylic electrophiles.…”

mentioning

confidence: 99%

“…[18] At present, reagent-based protocols for the dehydroxyfluorination [19] of propargylic alcohols remain the state-of-the-art methods for the preparation of propargylic fluorides,a nd, to the best of our knowledge,c atalytic nucleophilic fluorination reactions of propargylic electrophiles have not been reported. When considering the use of fluoride anions in propargylic substitution reactions, [20] our attention was drawn to as tudy by Murahashi and co-workers on the copper(I)-catalyzed amination of propargylic electrophiles.…”

mentioning

confidence: 99%

Catalytic Nucleophilic Fluorination of Secondary and Tertiary Propargylic Electrophiles with a Copper–N‐Heterocyclic Carbene Complex

Cheng

Cordier

2015

Angewandte Chemie

View full text Add to dashboard Cite

Acatalytic method for the nucleophilic fluorination of propargylic electrophiles is described. Our protocol involves the use of aC u(NHC) complex as the catalyst and is suitable for the preparation of secondary and tertiary propargylic fluorides without the formation of isomeric fluoroallenes. Preliminary mechanistic investigations suggest that fluorination proceeds via copper acetylides and that cationic species are involved.Compounds containing CÀFb onds are of vital importance to the pharmaceutical [1] and agrochemical industries, [2] positron-emission tomography, [3] and materials science.[4] Catalytic fluorination has been the focus of many investigations, [5] in which either electrophilic or nucleophilic fluorine sources have been used.[6] Despite these significant advances,catalytic nucleophilic fluorination remains ac hallenge,p articularly at C(sp 3 )c enters. [7] Theh igh charge density of unsolvated fluoride anions imparts high nucleophilicity but also strong basicity, [8] thus enabling elimination pathways to alkenes. Hydrogen bonding to fluoride anions by protic solvents limits the formation of alkene by-products owing to reduced basicity [9] but significantly reduces fluoride nucleophilicity. This dichotomy represents au nique challenge for catalysis, and the catalytic nucleophilic fluorination of comparatively simple non-activated primary alkyl electrophiles is still relatively underdeveloped.[10] Strategies for installing fluoride substituents into organic molecules equipped with functional groups for subsequent synthetic elaboration are of notable utility.T om eet this objective,t ransition-metal-catalyzed methods for the nucleophilic fluorination of allylic electrophiles,with Pd, [11] Ir, [12] Rh, [13] or Cu [14] complexes as catalysts, have received considerable attention [Eq. (1)].These approaches exploit the electrophilicity of metal-pallyl intermediates and have been elegantly engineered to overcome significant challenges,i ncluding elimination to form dienes,t he reversibility of CÀFb ond formation, [15] and regioselectivity (formation of branched or linear allylic fluorides). By contrast, catalytic methods for preparing propargylic fluorides remain underrepresented.[16] Propargylic fluorides are important motifs in biologically active compounds [17] and are used as synthetic precursors to fluorinated analogues of fluoroglycosides and antiviral, antifungal, and anticancer agents.[18] At present, reagent-based protocols for the dehydroxyfluorination [19] of propargylic alcohols remain the state-of-the-art methods for the preparation of propargylic fluorides,a nd, to the best of our knowledge,c atalytic nucleophilic fluorination reactions of propargylic electrophiles have not been reported. When considering the use of fluoride anions in propargylic substitution reactions, [20] our attention was drawn to as tudy by Murahashi and co-workers on the copper(I)-catalyzed amination of propargylic electrophiles.[21a] This strategy for propargylic substitution under copper catalysis has sin...

show abstract

Recent advances in copper-catalyzed propargylic substitution

Cited by 240 publications

References 82 publications

Desilylation‐Activated Propargylic Transformation: Enantioselective Copper‐Catalyzed [3+2] Cycloaddition of Propargylic Esters with β‐Naphthol or Phenol Derivatives

Desilylation‐Activated Propargylic Transformation: Enantioselective Copper‐Catalyzed [3+2] Cycloaddition of Propargylic Esters with β‐Naphthol or Phenol Derivatives

Highly Enantioselective Synthesis of Propargyl Amide with Vicinal Stereocenters through Ir‐Catalyzed Hydroalkynylation

Catalytic Nucleophilic Fluorination of Secondary and Tertiary Propargylic Electrophiles with a Copper–N‐Heterocyclic Carbene Complex

Contact Info

Product

Resources

About