A Powerful Chiral Counteranion Motif for Asymmetric Catalysis
Angewandte Chemie International EditionPublished 13 May 2009Open access
Pilar Garcı́a Garcı́a, Frank Lay, Patricia García‐García, Constantinos Rabalakos, Benjamin List
Citations277
SJR quartileQ1
SJR score5.55
SNIP2.47
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
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.
Abstract
Room to swing a cat: A chiral disulfonimide has been designed as a powerful new motif for asymmetric catalysis. As a first illustration, a highly efficient and enantioselective Mukaiyama aldol reaction has been developed (see scheme). The actual catalyst is proposed to be an N-silyl imide which is generated in situ.
Keywords
Chemistry
NatureThe advent and development of organocatalysis
2,351 Citations2008David W. C. MacMillan
My opinion on why the field of organocatalysis has blossomed so dramatically over the past decade is presented.
ScienceReversible, Metal-Free Hydrogen Activation
2,147 Citations2006Gregory C. Welch, Ronan R. San Juan +2 more
The compound (C6H2Me3)2PH(C 6F4)BH(C6F5)2 (Me, methyl), which is derived through an unusual reaction involving dimesitylphosphine substitution at a para carbon of tris(pentafluorophenyl) borane, cleanly loses H2 at temperatures above 100°C.
Angewandte Chemie International EditionEnantioselective Mannich‐Type Reaction Catalyzed by a Chiral Brønsted Acid
1,641 Citations2004Takahiko Akiyama, Junji Itoh +2 more
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.
ScienceA Powerful Chiral Counterion Strategy for Asymmetric Transition Metal Catalysis
902 Citations2007Gregory L. Hamilton, Eun Joo Kang +2 more
It is shown that the chiral counterion can be combined additively with chiral ligands to enable an asymmetric transformation that cannot be achieved by either method alone.
Angewandte Chemie International Edition“Designer Acids”: Combined Acid Catalysis for Asymmetric Synthesis
680 Citations2005Hisashi Yamamoto, Kentaro Futatsugi
Combining Lewis and Brønsted acids will bring out their inherent reactivity by associative interaction, and also provide more-organized structures that allow an effective asymmetric environment.
Journal of the American Chemical SocietyChiral Counteranions in Asymmetric Transition-Metal Catalysis: Highly Enantioselective Pd/Brønsted Acid-Catalyzed Direct α-Allylation of Aldehydes
614 Citations2007Santanu Mukherjee, Benjamin List
This work has developed a highly enantioselective Pd/chiral acid-catalyzed α-allylation of α-branched aldehydes with an allyl amine as the allylating species that creates all-carbon quaternary stereogenic centers in high yields and enantiosity.
Angewandte Chemie International EditionAsymmetric Counteranion‐Directed Catalysis
550 Citations2006Sonja Mayer, Benjamin List
Angewandte ChemieEnantioselective Mannich‐Type Reaction Catalyzed by a Chiral Brønsted Acid
550 Citations2004Takahiko Akiyama, Junji Itoh +2 more
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.
Focus on CatalystsAsymmetric organocatalysis – from biomimetic concepts to applications in asymmetric synthesis
397 Citations2005
Canadian Journal of ChemistryHydrolysis of esters of oxy acids: p<i>K</i><sub>a</sub> values for strong acids; Brønsted relationship for attack of water at methyl; free energies of hydrolysis of esters of oxy acids; and a linear relationship between free energy of hydrolysis and p<i>K</i><sub>a</sub> holding over a range of 20 p<i>K</i> units
382 Citations1978J. Peter Guthrie
Angewandte Chemie International EditionAsymmetric Brønsted Acid Catalysis: Enantioselective Nucleophilic Substitutions and 1,4‐Additions
349 Citations2007Magnus Rueping, Boris J. Nachtsheim +2 more
Inorganic ChemistrySynthesis, properties, and reactions of bis((trifluoromethyl)sulfonyl) imide, (CF3SO2)2NH
336 Citations1984Jerry Foropoulos, Darryl D. DesMarteau
Journal of the American Chemical SocietyCatalytic, Enantioselective Aldol Additions with Methyl and Ethyl Acetate O-Silyl Enolates: A Chiral Tridentate Chelate as a Ligand for Titanium(IV)
282 Citations1994Erick M. Carreira, Robert A. Singer +1 more
Journal of the American Chemical Society<i>C</i><sub>2</sub>-Symmetric Copper(II) Complexes as Chiral Lewis Acids. Catalytic Enantioselective Aldol Additions of Silylketene Acetals to (Benzyloxy)acetaldehyde
244 Citations1996David A. Evans, Jerry A. Murry +1 more
Angewandte ChemieKombinierte Säurekatalyse in der asymmetrischen Synthese durch “Designer‐Säuren”
224 Citations2005Hisashi Yamamoto, Kentaro Futatsugi
Tetrahedron LettersEnantioselective Mukaiyama-aldol and aldol-dihydropyrone annulation reactions catalyzed by a tryptophan-derived oxazaborolidine
217 Citations1992E. J. Corey, Charles L. Cywin +1 more
Angewandte ChemieAsymmetrische Gegenanion‐vermittelte Katalyse
204 Citations2006Sonja Mayer, Benjamin List
Journal of the American Chemical SocietyCatalytic asymmetric aldol reactions. Use of a chiral (acyloxy)borane complex as a versatile Lewis-acid catalyst
182 Citations1991Kyoji Furuta, Tohru Maruyama +1 more
Journal of the American Chemical SocietyPyridinium 1,1′-Binaphthyl-2,2′-disulfonates as Highly Effective Chiral Brønsted Acid−Base Combined Salt Catalysts for Enantioselective Mannich-Type Reaction
178 Citations2008Manabu Hatano, Toshikatsu Maki +3 more
An efficient enantioselective catalysis in the Mannich-type reactions of diketones and ketoester equivalents with aldimines was developed using chiral 1-achiral 2,6-diarylpyridine combined salts, which acted as convenient chiral tailor-made Brønsted acid-base organocatalysts in situ.
Journal of the American Chemical SocietyNew catalysts for the asymmetric aldol reaction: chiral boranes prepared from .alpha.,.alpha.-disubstituted glycine arenesulfonamides
178 Citations1991Emma R. Parmee, Orin Tempkin +2 more
Journal of the American Chemical SocietyEnantioselective and diastereoselective catalysis of the Mukaiyama aldol reaction: ene mechanism in titanium-catalyzed aldol reactions of silyl enol ethers
170 Citations1993Köichi Mikami, Satoru Matsukawa
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
Journal of the American Chemical SocietyLewis Base Activation of Lewis Acids. Addition of Silyl Ketene Acetals to Aldehydes
153 Citations2002Scott E. Denmark, Thomas Wynn +1 more
The weak Lewis acid silicon tetrachloride can be activated by catalytic amounts of the chiral bisphosphoramide (R,R)-3 to form a highly reactive, chiral trichlorosilyl cation which is an extremely effective promoter of aldol addition reactions between aldehydes and silyl ketene acetals.
TetrahedronTrimethylsilyl bis(trifluoromethanesulfonyl)imide as a tolerant and environmentally benign Lewis acid catalyst of the Diels–Alder reaction
144 Citations2002B. Mathieu, Léon Ghosez
Angewandte ChemieAsymmetrische Brønsted‐Säure‐Katalyse: enantioselektive nucleophile Substitutionen und 1,4‐Additionen
142 Citations2007Magnus Rueping, Boris J. Nachtsheim +2 more
Tetrahedron LettersN-Trimethylsilyl-bis(trifluoromethanesulfonyl)imide: a better carbonyl activator than trimethylsilyl triflate
123 Citations1997B. Mathieu, Léon Ghosez
Angewandte Chemie International EditionHighly Diastereo‐ and Enantioselective Mukaiyama Aldol Reactions Catalyzed by Hydrogen Bonding
118 Citations2006Jeff D. McGilvra, Aditya K. Unni +2 more
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 SocietyHighly <i>anti</i>-Selective Catalytic Asymmetric Aldol Reactions
99 Citations2000Haruro Ishitani, Yasuhiro Yamashita +2 more
TetrahedronA rapid injection NMR study of the chelation controlled Mukaiyama aldol addition: TiCl4 versus LiClO4 as the Lewis acid
71 Citations1992Manfred T. Reetz, Burkhard Raguse +4 more
Chemistry - An Asian JournalThe Catalytic Acylcyanation of Imines
70 Citations2008Subhas Chandra Pan, Benjamin List
A highly enantioselective version has been established, culminating in the first organocatalytic asymmetric three-component Strecker reaction, and a novel cyclic amidine was obtained from the reaction of acetyl cyanide with ketimines.
SynlettPhosphoric Acid Diesters as Efficient Catalysts for Hydroaminations of Nonactivated Alkenes and an Application to Asymmetric Hydroaminations
66 Citations2008Lutz Ackermann, Andreas Althammer
Advanced Synthesis & CatalysisBrønsted Acid‐Catalyzed Three‐Component Hosomi–Sakurai Reactions
60 Citations2008Daniela Kampen, Arnaud Ladépêche +2 more
Tetrahedron AsymmetryCatalytic asymmetric aldol reaction of the silyl enol ether of acetic acid thioester with aldehydes using chiral tin(II) Lewis acid
57 Citations1991Shū Kobayashi, M. Furuya +2 more
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.
Angewandte ChemieEnantioselective Activation of Aldehydes by Chiral Phosphoric Acid Catalysts in an Aza‐ene‐type Reaction between Glyoxylate and Enecarbamate
49 Citations2008Masahiro Terada, Kazuyo Soga +1 more
Synthesis<i>o</i>-Benzenedisulfonimide as a Soft, Efficient, and Recyclable Catalyst for the Acylation of Alcohols, Phenols, and Thiols under Solvent-Free Conditions: Advantages and Limitations
39 Citations2008Margherita Barbero, Silvano Cadamuro +2 more
Angewandte ChemieHighly Diastereo‐ and Enantioselective Mukaiyama Aldol Reactions Catalyzed by Hydrogen Bonding
27 Citations2006Jeff D. McGilvra, Aditya K. Unni +2 more
