<i>N</i>-Triflylthiophosphoramide Catalyzed Enantioselective Mukaiyama Aldol Reaction of Aldehydes with Silyl Enol Ethers of Ketones
Organic LettersPublished 13 May 2010Open access
Cheol Hong Cheon, Hisashi Yamamoto
Citations77
Generate an AI Snapshot to get a quick, structured summary of this paper.
Study Snapshot
ObjectiveStudy objective
MethodsResearch methodology
PopulationPopulation studied
Sample sizeSample sizes
OutcomesStudy outcomes here
ResultsStudy results comes here
LimitationsResearch study limitations comes here
A concise AI-generated summary of the paper will appear here once you click Generate AI Snapshot.
TL;DR
The first Brønsted acid catalyzed asymmetric Mukaiyama aldol reaction of aldehydes using silyl enol ethers of ketones as nucleophiles has been reported, with excellent yields and good to excellent enantioselectivities.
Abstract
The first Brønsted acid catalyzed asymmetric Mukaiyama aldol reaction of aldehydes using silyl enol ethers of ketones as nucleophiles has been reported. A variety of aldehydes and silyl enol ethers of ketones afforded the aldol products in excellent yields and good to excellent enantioselectivities. Mechanistic studies revealed that the actual catalyst may be changed from the silylated Brønsted acid to the Brønsted acid itself depending on the reaction temperature.
Keywords
Chemistry
Angewandte Chemie International EditionEnantioselective Mannich‐Type Reaction Catalyzed by a Chiral Brønsted Acid
1,641 Citations2004Takahiko Akiyama, Junji Itoh +2 more
Journal of the American Chemical SocietyChiral Brønsted Acid-Catalyzed Direct Mannich Reactions via Electrophilic Activation
1,581 Citations2004Daisuke Uraguchi, Masahiro Terada
It was found that the phosphoric acid derivatives of general structure 1 serve as highly effective catalysts for the direct addition of acetyl acetone to N-Boc-protected arylimines and functions as an excellent catalyst.
Chemical CommunicationsBinaphthol-derived phosphoric acid as a versatile catalyst for enantioselective carbon–carbon bond forming reactions
1,025 Citations2008Masahiro Terada
Binaphthol-derived monophosphoric acids have been designed as novel chiral Brønsted-acid catalysts, which function as efficient enantioselective catalysts for a variety of organic transformations, especially for carbon-carbon bond forming reactions.
Accounts of Chemical Researchπ-Nucleophilicity in Carbon−Carbon Bond-Forming Reactions
1,004 Citations2002Herbert Mayr, Bernhard Kempf +1 more
This Account adjusts the N and s parameters of all presently characterized pi-nucleophiles (arenes, alkenes, organometallics) to the new parametrization and illustrates how to employ the resulting reactivity scales for analyzing synthetic and mechanistic problems in organic and macromolecular chemistry.
Journal of the American Chemical SocietyOrganocatalytic Synthesis of Spiro[pyrrolidin-3,3′-oxindoles] with High Enantiopurity and Structural Diversity
572 Citations2009Xiaohua Chen, Qiang Wei +3 more
The straightforward construction of spirooxindole skeletons with high stereo- and regioselectivity suggests a new avenue to medicinal chemistry and diversity-oriented synthesis.
Journal of the American Chemical SocietyDesign of Chiral <i>N</i>-Triflyl Phosphoramide as a Strong Chiral Brønsted Acid and Its Application to Asymmetric Diels−Alder Reaction
506 Citations2006Daisuke Nakashima, Hisashi Yamamoto
A highly reactive and acidic chiral Brønsted acid catalyst, chiral N-triflyl phosphoramide, was developed and highly enantioselective Diels-Alder reaction of alpha,beta-unsaturated ketone with silyloxydiene was demonstrated.
Journal of the American Chemical SocietyChiral Brønsted Acid-Catalyzed Enantioselective Three-Component Povarov Reaction
396 Citations2009Hua Liu, Guillaume Dagousset +3 more
The three-component Povarov reaction of aldehydes, anilines, and benzyl N-vinylcarbamate 4 in the presence of 0.1 equiv of chiral phosphoric acid afforded cis-2,4-disubstituted tetrahydroquinolines in good yields and excellent enantiomeric excesses.
Journal of the American Chemical SocietyMetal−Brønsted Acid Cooperative Catalysis for Asymmetric Reductive Amination
341 Citations2009Chaoqun Li, Barbara Villa‐Marcos +1 more
Direct reductive amination of a wide range of ketones has been accomplished by the cooperative catalysis of an Ir(III)-diamine complex and a chiral phosphoric acid or its conjugate base.
Journal of the American Chemical SocietyDirect Catalytic Asymmetric Synthesis of Cyclic Aminals from Aldehydes
284 Citations2008Xu Cheng, Sreekumar Vellalath +2 more
A highly enantioselective Brønsted acid catalyzed direct synthesis of cyclic aminals from aldehydes has been developed and has been applied to the first asymmetric synthesis of several antihypertensive aminal drugs including (R)-Thiabutazide.
Angewandte Chemie International EditionA Powerful Chiral Counteranion Motif for Asymmetric Catalysis
277 Citations2009Pilar Garcı́a Garcı́a, Frank Lay +3 more
A chiral disulfonimide has been designed as a powerful new motif for asymmetric catalysis and a highly efficient and enantioselective Mukaiyama aldol reaction has been developed.
Journal of the American Chemical SocietyA Brønsted Acid Catalyst for the Enantioselective Protonation Reaction
253 Citations2008Cheol Hong Cheon, Hisashi Yamamoto
A highly reactive and robust chiral Brønsted acid catalyst, chiral N-triflyl thiophosphoramide, was developed and the first metal-free BrøNsted acid catalyzed enantioselective protonation reaction of silyl enol ethers was demonstrated.
Journal of the American Chemical SocietyBrønsted Acid-Catalyzed Desymmetrization of <i>meso</i>-Aziridines
227 Citations2007Emily B. Rowland, Gerald B. Rowland +2 more
Preliminary mechanistic studies indicate that the active catalytic species is a chiral silane that is generated in situ, and the formation of the products in excellent yield and enantioselectivity.
Angewandte Chemie International EditionEnantioselective 1,3‐Dipolar Cycloaddition of Nitrones with Ethyl Vinyl Ether: The Difference between Brønsted and Lewis Acid Catalysis
200 Citations2008Peng Jiao, Daisuke Nakashima +1 more
Journal of the American Chemical SocietyHighly Enantioselective Organocatalytic Biginelli and Biginelli-Like Condensations: Reversal of the Stereochemistry by Tuning the 3,3′-Disubstituents of Phosphoric Acids
193 Citations2009Nan Li, Xiaohua Chen +4 more
3,3'-Di(triphenylsilyl) binaphthol-derived phosphoric acid afforded Biginelli-like reactions of a broad scope of aldehydes and enolizable ketones with benzylthiourea, giving structurally diverse dihydropyrimidinethiones with excellent optical purity.
Angewandte Chemie International EditionBrønsted Acid Catalyzed Enantioselective Three‐Component Reaction Involving the α Addition of Isocyanides to Imines
173 Citations2009Tao Yue, Mei‐Xiang Wang +3 more
It was reported that a chiral phosphoric acid is able to catalyze the three-component reaction of aldehydes, anilines, and alpha -isocyanoacetamides, leading to 2-(1-aminoalkyl)-5- aminooxazoles in excellent yields and moderate to good enantioselectivities.
Organic LettersBenzothiazoline: Highly Efficient Reducing Agent for the Enantioselective Organocatalytic Transfer Hydrogenation of Ketimines
173 Citations2009Chen Zhu, Takahiko Akiyama
Angewandte Chemie International EditionDirect Catalytic Asymmetric Three‐Component Kabachnik–Fields Reaction
170 Citations2008Xu Cheng, Richard Goddard +2 more
This work shows that racemic a-branched aldehydes, in the presence of a new chiral phosphoric acid catalyst, directly react with p-anisidine and a phosphite to furnish b-brANChed a-amino phosphonates highly diastereoselectively and enantioselective by a dynamic kinetic resolution.
Angewandte Chemie International EditionEnantioselective Activation of Aldehydes by Chiral Phosphoric Acid Catalysts in an Aza‐ene‐type Reaction between Glyoxylate and Enecarbamate
156 Citations2008Masahiro Terada, Kazuyo Soga +1 more
TetrahedronTrimethylsilyl bis(trifluoromethanesulfonyl)imide as a tolerant and environmentally benign Lewis acid catalyst of the Diels–Alder reaction
144 Citations2002B. Mathieu, Léon Ghosez
Organic LettersHighly Enantioselective Hydrogenation of Enamides Catalyzed by Chiral Phosphoric Acids
133 Citations2009Guilong Li, Jon C. Antilla
A highly enantioselective hydrogenation of enamides catalyzed by a dual chiral-achiral acid system was developed by employing a substoichiometric amount of a chiral phosphoric acid and acetic acid.
Organic LettersChiral Brønsted Acid-Catalyzed Enantioselective Multicomponent Mannich Reaction: Synthesis of <i>anti</i>-1,3-Diamines Using Enecarbamates as Nucleophiles
119 Citations2009Guillaume Dagousset, Fleur Drouet +2 more
Reaction of aldehydes 2, anilines 3, and enecarbamates 4 in dichloromethane in the presence of EtOH and a catalytic amount of chiral phosphoric acid afforded the Mannich adducts which were in situ reduced to anti-1,2-disubstituted 1,3-diamines 1 in excellent diastereoselectivity and enantioselectivities.
Angewandte Chemie International EditionHighly Diastereo‐ and Enantioselective Mukaiyama Aldol Reactions Catalyzed by Hydrogen Bonding
118 Citations2006Jeff D. McGilvra, Aditya K. Unni +2 more
Organic LettersHydrogen Bond Catalyzed Enantioselective Vinylogous Mukaiyama Aldol Reaction
114 Citations2005Vijaya Bhasker Gondi, Michel Gravel +1 more
The concept of hydrogen bonding catalysis was extended to the vinylogous Mukaiyama aldol reaction, which gives rapid access to polyketide derivatives, and regiospecifically to produce the addition products in good yields and enantiomeric excesses.
Organic LettersStrong Counteranion Effects on the Catalytic Activity of Cationic Silicon Lewis Acids in Mukaiyama Aldol and Diels−Alder Reactions
113 Citations2005Kenji Hara, Ryuto Akiyama +1 more
A toluene-coordinated silyl borate, [Et3Si(toluene)]B(C6F5)4, demonstrated catalytic activities significantly higher than those of Me3SiOTf and Me3 SiNTf2 in Mukaiyama aldol and Diels-Alder reactions.
Organic & Biomolecular ChemistryA versatile catalyst for asymmetric reactions of carbonyl groups working purely by activation through hydrogen bonding: Mukaiyama-aldol, hetero Diels–Alder and Friedel–Crafts reactions
111 Citations2005Wei Zhuang, Thomas B. Poulsen +1 more
It is shown that bis-triflamides or bis-nonaflamides of commercially available chiral diamines act as chiral Brønsted-acid catalysts, leading to the optically active products in moderate to excellent yields and with enantioselectivities up to 73% ee.
Journal of the American Chemical SocietyChiral Phosphoric Acid-Governed Anti-Diastereoselective and Enantioselective Hetero-Diels−Alder Reaction of Glyoxylate
103 Citations2009Norie Momiyama, Hideaki Tabuse +1 more
The diastereoselectivities presented are disparate to those previously reported for hetero-Diels-Alder reactions catalyzed by a chiral Lewis acid.
Chemistry - A European JournalAsymmetric Synthesis of 3‐Amino‐δ‐lactams and Benzo[<i>a</i>]quinolizidines by Catalytic Cyclization Reactions Involving Azlactones
95 Citations2009Jun Jiang, Jian Qing +1 more
The first asymmetric catalytic three-component cyclization reaction of cinnamaldehydes, primary amines, and azlactones is reported by using chiral Brønsted acid catalysts, which yields dihydropyridinones with high enantioselectivity.
Organic LettersHighly Efficient Asymmetric <i>Trans-</i>Selective Aziridination of Diazoacetamides and <i>N</i>-Boc-imines Catalyzed by Chiral Brønsted Acids
91 Citations2009Xiaofei Zeng, Xin Zeng +3 more
A clean and fast aziridination of diazoacetamides with N-Boc-imines, as well as N-Cbz-imine, catalyzed by chiral phosphoric acid (R)-5g in DCM at room temperature was developed.
Angewandte Chemie International EditionDiastereoselective and Enantioselective Synthesis of Tertiary α‐Hydroxy Phosphonates through Hydrogen‐Bond Catalysis
74 Citations2008Vijaya Bhasker Gondi, Koji Hagihara +1 more
This survey showed that many common hydrogen-bond donors, without additional structural optimization, accelerated the Mukaiyama aldol reaction between N,O-ketene acetal 13 and acetyl phosphonate 14, showing an improved diastereoselectivity over the uncatalyzed reaction, although they varied widely in their ability to induce enantiselectivity.
Organic LettersAsymmetric Hydrocyanation of Hydrazones Catalyzed by in Situ Formed <i>O</i>-Silylated BINOL-Phosphate: A Convenient Access to Versatile α-Hydrazino Acids
59 Citations2009Alexandru Zamfir, Svetlana B. Tsogoeva
A first organocatalytic enantioselective route was developed for the conversion of readily prepared and air stable aliphatic hydrazones to synthetically valuable alpha-hydrazinonitriles, and this BINOL-phosphate catalyzed Strecker-type reaction provides a new practical and direct route to alpha-Hydrazino acids of synthetic and biological importance.
Chemical CommunicationsCrucial role of the ligand of silyl Lewis acid in the Mukaiyama aldol reactionElectronic supplementary information (ESI) available: experimental section. See http://www.rsc.org/suppdata/cc/b2/b203838b/
52 Citations2002Kazuaki Ishihara, Yukihiro Hiraiwa +1 more
The Me 3SiX-induced Mukaiyama aldol reaction proceeds through each catalytic cycle under the influence of X-: the silyl group of Me3SiNTf2 does not release from - NTf2 and that of sily l enol ether intermolecularly transfers to the product.
Tetrahedron LettersA new Brønsted acid derived from squaric acid and its application to Mukaiyama aldol and Michael reactions
25 Citations2009Cheol Hong Cheon, Hisashi Yamamoto