Palladium-catalyzed Asymmetric Arylation Research Articles

Enantioselective synthesis of α-amino ketones through palladium-catalyzed asymmetric arylation of α-keto imines.

Chiral α-amino ketones are common structural motifs in natural products and pharmaceuticals, as well as important synthons in organic synthesis. Thus, establishing efficient methods for preparing compounds with these privileged scaffolds is an important endeavor in synthetic chemistry. Herein we disclose a new catalytic asymmetric approach for the synthesis of chiral α-amino ketones through a chiral palladium-catalyzed arylation reaction of in situ generated challenging α-keto imines from previously unreported C-acyl N-sulfonyl-N,O-aminals, with arylboronic acids. The current reaction offers a straightforward approach to the asymmetric synthesis of acyclic α-amino ketones in a practical and highly stereocontrolled manner. Meanwhile, the multiple roles of the chiral Pd(ii) complex catalyst in the reaction were also reported.

Spiro indane-based phosphine–oxazoline ligands for palladium-catalyzed asymmetric arylation of cyclic N-sulfonyl imines

Palladium complexes of indane-based phosphine–oxazoline ligands with a spirocarbon stereogenic center were examined for asymmetric addition of arylboronic acids to cyclic N-sulfonyl imines. Excellent reaction activities (up to 99% yield) and enantioselectivities (up to 99% ee) were obtained with a broad scope of substrate.

Palladium-Catalyzed Asymmetric Arylation of C(sp(3))-H Bonds of Aliphatic Amides: Controlling Enantioselectivity Using Chiral Phosphoric Amides/Acids.

Enantioselective arylation of secondary β-C(sp(3))-H bonds of 8-aminoquinoline amides was realized with a palladium catalyst. Chiral phosphoric amides and acids were used for the first time to control the stereoselectivity at the C-H bond cleavage step in the C-H activation reactions.

Pd(ii)-catalyzed asymmetric addition of arylboronic acids to cyclic N-sulfonyl ketimine esters and a DFT study of its mechanism

A highly efficient palladium-catalyzed asymmetric arylation of cyclic ketimine esters is developed, which provides the desired product in up to 99% yield with up to 99% ee. The mechanism of enantioselection is studied using DFT calculation.

Ligand-Controlled Asymmetric Arylation of Aliphatic α-Amino Anion Equivalents

A palladium-catalyzed asymmetric arylation of 9-aminofluorene-derived imines using a chiral dialkylbiaryl phosphine as the supporting ligand has been developed. This transformation allows for enantioselective access to a diverse range of α-branched benzylamines.

ChemInform Abstract: Palladium-Catalyzed Asymmetric Arylation of 4,7-Dihydro-1,3-dioxepin. Catalytic Asymmetric Synthesis of γ-Butyrolactone Derivatives.

The palladium-catalyzed asymmetric arylation of 4,7-dihydro-1,3-dioxepin 1d has been shown to give 2d-h (up to 75% ee), which can be readily converted to γ-butyrolactone derivatives. The important role of molecular sieves in the asymmetric Heck reaction has been also clarified.

Palladium-catalyzed asymmetric arylation of 2,3-dihydrofuran with aryl triflates in water in the presence of surfactants

Abstract Palladium-catalyzed asymmetric arylation of 2,3-dihydrofuran with aryl triflates occurred in water in the presence of surfactants under very mild conditions. In the presence of C 16 H 33 N + Me 2 (CH 2 ) 3 SO 3 − (HDAPS) as the surfactant and Binap as the chiral ligand, enantiomeric excess up to 67% with a conversion of 73% after 2 h were obtained.

Palladium-catalyzed asymmetric arylation, vinylation, and allenylation of tert-cyclobutanols via enantioselective C-C bond cleavage.

A novel enantioselective C-C bond cleavage has been achieved using palladium catalysts and chiral N,P-bidentate ligands in the asymmetric arylation, vinylation, and allenylation of tert-cyclobutanols. In these reactions, the enantioselective beta-carbon elimination of Pd(II) alcoholate formed in situ is the key step. Treatment of tert-cyclobutanols with arylating reagents in toluene in the presence of Pd(OAc)(2), a chiral ferrocene-containing N,P-bidentate ligand, and Cs(2)CO(3) affords optically active gamma-arylated ketones in excellent yields with high enantioselectivity (up to 95% ee). When vinylating reagents are used in place of arylating ones, the asymmetric vinylation also proceeds to afford optically active gamma-vinylated ketones in high yields with good to high enantioselectivity. When propargylic acetates are used, which are known to generate (sigma-allenyl)palladium complexes with Pd(0) species, asymmetric allenylation occurs to afford optically active gamma-allenylated ketones in moderate to good yields with moderate to high enantioselectivity.

Palladium-catalyzed asymmetric arylation of 4,7-dihydro-1,3-dioxepin. Catalytic asymmetric synthesis of γ-butyrolactone derivatives

The palladium-catalyzed asymmetric arylation of 4,7-dihydro-1,3-dioxepin 1d has been shown to give 2d-h (up to 75% ee), which can be readily converted to γ-butyrolactone derivatives. The important role of molecular sieves in the asymmetric Heck reaction has been also clarified.

Palladium-catalyzed asymmetric arylation of 2,3-dihydrofuran with phenyl triflate. A novel asymmetric catalysis involving a kinetic resolution process

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPalladium-catalyzed asymmetric arylation of 2,3-dihydrofuran with phenyl triflate. A novel asymmetric catalysis involving a kinetic resolution processFumiyuki Ozawa, Akihiko Kubo, Yonetatsu Matsumoto, Tamio Hayashi, Eriko Nishioka, Kazunori Yanagi, and Kohichi MoriguchiCite this: Organometallics 1993, 12, 10, 4188–4196Publication Date (Print):October 1, 1993Publication History Published online1 May 2002Published inissue 1 October 1993https://doi.org/10.1021/om00034a064RIGHTS & PERMISSIONSArticle Views1751Altmetric-Citations224LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (2 MB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Palladium-catalyzed asymmetric arylation of 2,3-dihydrofuran: 1,8-Bis(dimethylamino)naphthalene as an efficient base

Reaction of 2,3-dihydrofuran with aryl triflate ( 1) in the presence of a base and a palladium catalyst, generated in situ from Pd(OAc) 2 and (R)-BINAP, gave (R)-2-aryl-2,3-dihydrofuran ( 2) and a small amount of (S)-2-aryl-2,5-dihydrofuran ( 3). The enantiomeric purity of major product 2 was strongly affected by the base. 1,8-Bis(dimethylamino)naphthalene (proton sponge) as a highly basic and sterically demanding amine gave (R)-2 in high enantioselectivities ( > 96-87% ee) for a variety of aryl triflates.