Catalytic asymmetric aldol reaction:  reaction of aldehydes with isocyanoacetate catalyzed by a chiral ferrocenylphosphine-gold(I) complex

Ito, Yoshihiko; Sawamura, Masaya; Hayashi, Tamio

doi:10.1021/ja00280a056

Cited by 779 publications

(409 citation statements)

References 0 publications

Supporting

Mentioning

373

Contrasting

Unclassified

Order By: Relevance

“…Additionally, the possibility to tune their electronic and steric properties by variation of substituents [6], make carbenes versatile ligands for transition metal catalysts [7]. Since the Au(I) catalyzed asymmetric aldol reaction was published in the late 1980s [8], the use of Au (I) complexes in catalysis has received a lot of attention [9,10]. The first NHC substituted neutral and cationic gold(I) complexes were published in 1989 [11], and their application in catalysis stated in 2003 [12].…”

Section: Stable Carbenes; Carbene Complexes; Goldmentioning

confidence: 99%

Cyclic (alkyl)(amino)carbene gold(I) complexes: A synthetic and structural investigation

Frey

Dewhurst

Kousar

et al. 2008

Journal of Organometallic Chemistry

131

101

View full text Add to dashboard Cite

A series of mono-and dicarbene gold(I) complexes of types Au(CAAC)(Cl) [CAAC = cyclic (alkyl) (amino)carbene] (1) and [Au(CAAC) 2 ] + [X] -(X = Cl, AuCl 2 ) (2) have been prepared through reaction of AuCl(SMe 2 ) with free carbenes a-e, and structurally characterized by single X-ray diffraction studies (1a, 1b, 2d, 2e). In addition two new free cyclic (alkyl)(amino)carbenes (c and e) have been synthesized. Keywords Stable Carbenes; Carbene Complexes; GoldFollowing the discovery of the first stable derivatives [1,2], singlet carbenes have received considerable attention as ligands for transition metals [3,4]. Carbenes feature a strong σ-donating ability, and strongly bind metal centers of high and low oxidation states [5]. Additionally, the possibility to tune their electronic and steric properties by variation of substituents [6], make carbenes versatile ligands for transition metal catalysts [7]. Since the Au(I) catalyzed asymmetric aldol reaction was published in the late 1980s [8], the use of Au (I) complexes in catalysis has received a lot of attention [9,10]. The first NHC substituted neutral and cationic gold(I) complexes were published in 1989 [11], and their application in catalysis stated in 2003 [12].We have already reported the synthesis and isolation of well-defined cyclic (alkyl)(amino) carbenes (CAAC) [13a], their use for the activation of small molecules [13b-d], their properties as ligand for transition metals [13e,f], and recently the preparation of a CAAC gold(I) complex, which allows for the catalytic formation of allenes, starting from enamines and alkynes [14]. This manuscript describes the synthesis and characterization of a series of Au(I) complexes, featuring one or two CAACs, depending on the bulkiness of the carbene ligand.The free carbenes (a-e) including the new ones (c and e) were readily prepared by deprotonation with LDA of the corresponding iminium salts; the latter were synthesized using the hydroiminiumation route [15] as shown in Scheme 1.The gold complexes 1a-d were then cleanly prepared by stirring the free carbenes a-d overnight in darkness in THF with AuCl(SMe 2 ), the same procedure used for the corresponding NHC complexes [16]. After removing the solvent under vacuum and washing with hexanes, the * To whom correspondence should be addressed. E-mail: gbertran@mail.ucr.edu Publisher's Disclaimer: This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. Under the same reaction conditions, a different behavior was observed for carbene e. In this case the reaction of a stoichiometric amount of e with AuCl(SMe 2 ) did not afford the expected mono-carbene gold c...

show abstract

Section: Stable Carbenes; Carbene Complexes; Goldmentioning

confidence: 99%

Cyclic (alkyl)(amino)carbene gold(I) complexes: A synthetic and structural investigation

Frey

Dewhurst

Kousar

et al. 2008

Journal of Organometallic Chemistry

131

101

View full text Add to dashboard Cite

show abstract

“…The earliest example of an enantioselective gold(I)-catalyzed transformation, the Hayashi-Ito aldol reaction, was proposed to rely on activation of the nucleophile as a chiral monophosphineAu(I) enolate. 2 In contrast, the majority of recently reported methods rely on the electrophilic nature of cationic bisphosphinegold(I) complexes to activate π-bonds toward addition of nucleophiles. 3 Therefore, the utility of chiral bisphosphinegold-(I) complexes would be signficantly extended if they could be employed as catalysts for enantioselective transformations that are not predicated on π-bond activation.…”

mentioning

confidence: 99%

Au(I)-Catalyzed Enantioselective 1,3-Dipolar Cycloadditions of Münchnones with Electron-Deficient Alkenes

2007

View full text Add to dashboard Cite

The first catalytic enantioselective 1,3-dipolar cycloaddition of münchnone dipoles with electron-deficent alkenes is described. The reaction is catalyzed by chiral bis(phosphine)gold(I) benzoate complexes and provides Δ-pyrrolines with excellent regio-, diastereo-, and enantioselectivity. The reaction is proposed to proceed through a 1,3-dipole generated by deprotonation of a gold(I)-activated azlactone.

show abstract

“…Structure of a gold-ferrocenyl derivative with Au-Fe bonding: Adrianov, Struchkov & Rossinskaya (1974). Use of ferrocenyl-gold compounds in asymmetric synthesis : Ito, Sawamura & Hayashi (1986).…”

mentioning

confidence: 99%

Chloro[diferrocenyl(phenyl)phosphine]gold(I)

Jones¹,

Erdbrügger²,

Hohbein³

et al. 1988

Acta Crystallogr C

View full text Add to dashboard Cite

Catalytic asymmetric aldol reaction: reaction of aldehydes with isocyanoacetate catalyzed by a chiral ferrocenylphosphine-gold(I) complex

Cited by 779 publications

References 0 publications

Cyclic (alkyl)(amino)carbene gold(I) complexes: A synthetic and structural investigation

Cyclic (alkyl)(amino)carbene gold(I) complexes: A synthetic and structural investigation

Au(I)-Catalyzed Enantioselective 1,3-Dipolar Cycloadditions of Münchnones with Electron-Deficient Alkenes

Chloro[diferrocenyl(phenyl)phosphine]gold(I)

Contact Info

Product

Resources

About