Masahiro Terada

Chiral phosphoric acids derived from axially chiral biaryls and related chiral Brønsted acids have emerged as an attractive and widely applicable class of enantioselective organocatalysts for a variety of organic transformations. This review focuses on recent achievements in the development of enantioselective transformations using these axially chiral phosphoric acids and their analogues as chiral Brønsted acid catalysts. The contents are arranged according to the specific types of carbon-carbo

Binaphthol-derived monophosphoric acids have been designed as novel chiral Brønsted-acid catalysts. The chiral phosphoric acids thus developed function as efficient enantioselective catalysts for a variety of organic transformations, especially for carbon-carbon bond forming reactions.

We present the first enantioselective catalysis of the Friedel−Crafts reaction via activation of electron-rich multiple bonds by a chiral Brønsted acid. The reaction of various indole derivatives with a broad range of substituted enecarbamates affords the corresponding Friedel−Crafts products in high yield and enantioselectivity.

Lowering the load: A very small amount of a binaphthol-derived monophosphoric acid organocatalyst accelerates an aza-ene-type reaction of N-benzoylimines with enecarbamates to provide β-aminoimines with high enantiomeric purity. This catalysis with a high substrate/catalyst(S/C) ratio provides a practical route to 1,3-diamine derivatives of synthetic and biological importance.

Weniger ist genug: Eine sehr kleine Menge eines von Binaphthol abgeleiteten Monophosphorsäure-Organokatalysators beschleunigt eine Aza-En-Reaktion zwischen N-Benzoyliminen und Encarbamaten zu hoch enantiomerenreinen β-Aminoiminen. Diese Katalyse mit hohem Substrat(S)/Katalysator(C)-Verhältnis macht 1,3-Diaminderivate von synthetischer und biologischer Bedeutung einfach zugänglich. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2001/2006/

A new strategy for designing chiral guanidine molecules is presented, which features the introduction of an axially chiral binaphthyl backbone. The axially chiral guanidine catalysts thus developed facilitated the highly enantioselective 1,4-addition reaction of 1,3-dicarbonyl compounds with a broad range of conjugated nitroalkenes and showed extremely high catalytic activity.

A newly designed axially chiral guanidine is found to function as an effective platform for asymmetric induction at the alpha-carbon of unsymmetrically substituted 1,3-dicarbonyl compounds. Highly efficient and enantioselective electrophilic amination of various 1,3-dicarbonyl compounds with azodicarboxylate was successfully achieved using the present chiral guanidine catalyst, which provides efficient access to the construction of nitrogen-substituted quaternary stereocenters in an optically ac

Abstract An inventive approach to the development of chiral Brønsted acid catalysis, to enable catalysts which possess strong acid functionalities, has been accomplished. Among the various organic Brønsted acids surveyed, phosphoric acids have become the focus of our attention as potential chiral Brønsted acid catalysts because of their unique structural and chemical features. The desirable features of phosphoric acids as chiral Brønsted acid catalysts are summarized as follows. 1) Phosphoric ac

Highly enantio- and diastereoselective direct aldol-type reaction of azlactones with oxocarbenium ions generated by protonation of vinyl ethers using a chiral phosphoric acid catalyst is presented. The method provides efficient access to biologically and pharmaceutically intriguing beta-hydroxy-alpha-amino acid derivatives having a quaternary stereogenic center at the alpha-carbon atom.

A chiral monophosphoric acid-catalyzed tandem aza-ene type reaction/cyclization cascade enabled the rapid construction of enantioenriched piperidine derivatives as key structural elements of numerous natural products. The potential of such cascade transformations is highlighted through their ability to achieve a rapid increase in molecular complexity from simple enecarbamates and a broad range of aldimines while also controlling three stereogenic centers in a highly diastereo- and enantioselecti

Double interaction does it: Highly enantio- and diastereoselective aza-ene-type reaction of glyoxylate with an enecarbamate is accomplished by using a binol-derived phosphoric acid catalyst (see scheme). DFT computational analysis revealed that two hydrogen bonds formed between the catalyst and the aldehyde are critical for the high enantioselectivity. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2008/z800232_s.pdf or from the aut

Abstract A highly enantioselective 1,2‐aza‐Friedel–Crafts reaction of N ‐ tert ‐butyldimethylsilylindole with N ‐ tert ‐butoxycarbonyl aromatic imines is demonstrated using a BINOL‐derived monophosphoric acid catalyst. The present approach provides efficient access to 3‐indolylmethaneamines with aryl substituents in excellent enantioselectivities (up to 98 % ee ). An inversion in the sense of enantioselection was found between monophosphoric acid catalysts bearing different substituents introduc

Chiral phosphoric acids derived from axially chiral biaryls and analogous chiral Bronsted acids have emerged as an attractive and widely applicable class of enantioselective organocatalysts for a variety of organic transformations. In this account article, we review our recent achievements and related works in the development of enantioselective carbon-carbon bond forming reactions using these axially chiral phosphoric acids and their analogues as chiral Bronsted acid catalysts. The contents are

The transformation of ortho-alkynylaryl ketones through a cyclization/enantioselective-reduction sequence in the presence of a chiral silver phosphate catalyst afforded 1H-isochromene derivatives in high yield with fairly good to high enantioselectivity. An asymmetric synthesis of the 9-oxabicyclo[3.3.1]nona-2,6-diene framework, which has been found in some biologically active molecules, is presented as a demonstration of the synthetic utility of this method.

Ace of Base: The first highly enantioselective direct vinylogous aldol reaction of dihalogenated or α-thio-substituted furanones with aldehydes utilizes an axially chiral guanidine base catalyst. The method provides facile access to enantioenriched γ-substituted butenolides. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note