Enantioselective Synthesis of Functionalized Nitrocyclopropanes by Organocatalytic Conjugate Addition of Bromonitroalkanes to α,β‐Unsaturated Enones
Chemistry - A European JournalPublished 10 December 2008
Jian Lv, Jiaming Zhang, Zhu Lin, Yongmei Wang
Citations91
SJR quartileQ1
SJR score0.98
SNIP0.84
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 general enantioselective synthesis of functionalized nitrocyclopropanes by organocatalytic conjugate addition of a variety of bromonitroalkanes to alpha,beta-unsaturated enone systems is presented.
Abstract
A general enantioselective synthesis of functionalized nitrocyclopropanes by organocatalytic conjugate addition of a variety of bromonitroalkanes to alpha,beta-unsaturated enone systems is presented. The process, efficiently catalyzed by the salts of 9-amino-9-deoxyepiquinine 1 d serves as a powerful approach to the preparation of synthetically and biologically important cyclopropanes with high levels of enantio- and diastereoselectivities. Since only 0.6 equivalents of bromonitromethane are used as a reagent, (S)-2 e is obtained enantiomerically pure by employing chiral 1 d as a highly efficient catalyst for its kinetic resolution (97 % ee at 51 % conversion, selectivity s=120).
Keywords
Chemistry
Chemical ReviewsStereoselective Cyclopropanation Reactions
1,783 Citations2003H. Lebel, Jean-François Marcoux +2 more
This review will focus mainly on the new methods that have appeared in the literature since 1989 for stereoselective cyclopropanation reactions from olefins: the halomethylmetal-mediated cycloalkane reactions, the transition metal-catalyzed decomposition of diazo compounds, and the nucleophilic addition-ring closure sequence.
Chemical ReviewsRecent Advances in Asymmetric Catalytic Metal Carbene Transformations
1,383 Citations1998Michael P. Doyle, David C. Forbes
Organic LettersHighly Enantioselective Conjugate Addition of Nitromethane to Chalcones Using Bifunctional Cinchona Organocatalysts
979 Citations2005Benedek Vakulya, Szilárd Varga +2 more
Cinchona alkaloid-derived chiral bifunctional thiourea organocatalysts were synthesized and applied in the Michael addition between nitromethane and chalcones with high ee and chemical yields.
ChemInformHighly Enantioselective Conjugate Addition of Nitromethane to Chalcones Using Bifunctional Cinchona Organocatalysts.
816 Citations2005Benedek Vakulya, Szilárd Varga +2 more
Chemical ReviewsBiosynthesis and Metabolism of Cyclopropane Rings in Natural Compounds
629 Citations2003Ludger A. Wessjohann, Wolfgang Brandt +1 more
TetrahedronSynthesis of cyclopropane containing natural products
615 Citations2001William A. Donaldson
Journal of the American Chemical SocietyGold(I)-Catalyzed Stereoselective Olefin Cyclopropanation
528 Citations2005Magnus J. Johansson, David J. Gorin +2 more
This reaction provided the basis for the use of a DTBM-SEGPHOS gold(I) complex as a catalyst in the enantioselective preparation of vinyl cyclopropanes with high cis-selectivity.
Journal of the American Chemical SocietyHighly Enantioselective Transfer Hydrogenation of α,β-Unsaturated Ketones
415 Citations2006Nolwenn J. A. Martin, Benjamin List
An efficient and highly enantioselective conjugate transfer hydrogenation of α,β-unsaturated ketones is described that is catalyzed by a salt made from tert-butyl valinate and a recently introduced powerful chiral phosphoric acid catalyst (TRIP).
Journal of the American Chemical SocietyEnantioselective Organocatalytic Cyclopropanations. The Identification of a New Class of Iminium Catalyst Based upon Directed Electrostatic Activation
371 Citations2005Roxanne K. Kunz, David W. C. MacMillan
This study outlines the identification of a new class of iminium catalyst based on the concept of directed electrostaticactivation (DEA) that exploits dual activation of ylide and enal substrates through a proposed electrostatic activation and stereodirected protocol.
Journal of the American Chemical SocietyOrganocatalytic Enantioselective Cascade Michael-Alkylation Reactions: Synthesis of Chiral Cyclopropanes and Investigation of Unexpected Organocatalyzed Stereoselective Ring Opening of Cyclopropanes
344 Citations2007Hexin Xie, Liansuo Zu +3 more
This investigation represents the first example of an organocatalyst-promoted ring opening of the cyclopropanes, whereas such reactions have been intensively explored by Lewis acid-based catalysis.
Angewandte Chemie International EditionHighly Asymmetric Michael Addition to α,β‐Unsaturated Ketones Catalyzed by 9‐Amino‐9‐deoxyepiquinine
316 Citations2006Jian‐Wu Xie, Wei Chen +8 more
Organic LettersOrganocatalytic Asymmetric Friedel−Crafts Alkylation of Indoles with Simple α,β-Unsaturated Ketones
306 Citations2007Giuseppe Bartoli, Marcella Bosco +4 more
The first general and highly enantioselective organocatalytic Friedel−Crafts alkylation of indoles with simple α,β-unsaturated ketones has been accomplished and a new catalyst amine salt is identified that exhibits high reactivity and selectivity for iminium ion catalysis.
Organic LettersReadily Accessible 9-epi-amino Cinchona Alkaloid Derivatives Promote Efficient, Highly Enantioselective Additions of Aldehydes and Ketones to Nitroolefins
276 Citations2007Séamus H. McCooey, Stephen J. Connon
Simple cinchona alkaloid derivatives, available via a one-pot procedure from commercially available starting materials, have been shown to promote highly enantio- and diastereoselective Michael-type addition reactions between enolizable carbonyl compounds and nitroalkenes of broad scope.
Angewandte Chemie International EditionEnantioselective Organocatalytic Cyclopropanation via Ammonium Ylides
275 Citations2004Charles D. Papageorgiou, Maria A. Cubillo de Dios +2 more
Angewandte Chemie International EditionEnantioselective Michael Addition to α,β‐Unsaturated Imides Catalyzed by a Bifunctional Organocatalyst
274 Citations2005Yasutaka Hoashi, Tomotaka Okino +1 more
Angewandte Chemie International EditionFascinating Natural and Artificial Cyclopropane Architectures
263 Citations2001Rüdiger Faust
Journal of the American Chemical SocietyOrganocatalytic Enantioselective Conjugate Additions to Enones
249 Citations2006Jian Wang, Hao Li +5 more
Conjugate addition reactions of a wide range of nucleophilic enol species with enones, catalyzed by a cinchona alkaloid derived thiourea organocatalyst, provide an efficient approach to the preparation of versatile building blocks possessing various functional groups.
Accounts of Chemical ResearchSynthesis and Properties of Cyclopropane-Derived Peptidomimetics
225 Citations2006Andreas Reichelt, Stephen F. Martin
This work invented trisubstituted cyclopropanes as novel peptidomimetics, anticipating that the Cyclopropane ring would locally orient the backbone and the corresponding amino acid side chain in the biologically active conformation.
Angewandte Chemie International EditionEnantioselective Catalytic Intramolecular Cyclopropanation using Modified Cinchona Alkaloid Organocatalysts
202 Citations2006Carin C. C. Johansson, Nadine Bremeyer +4 more
Advanced Synthesis & CatalysisA Simple Organocatalytic Enantioselective Cyclopropanation of α,β‐Unsaturated Aldehydes
196 Citations2007Ramón Rios, Henrik Sundén +4 more
A highly chemo- and enantioselective organocatalytic cyclopropanation of aldehydes with bromomalonate and 2-bromoacetoacetate esters is presented and gives access to 2-formylcyclopropanes in high yields and up to 99?% ee.
Organic LettersHighly Enantioselective Michael Addition of Cyclic 1,3-Dicarbonyl Compounds to α,β-Unsaturated Ketones
194 Citations2007Jian‐Hua Xie, Lei Yue +5 more
The highly enantioselective Michael addition of 1,3-cyclic dicarbonyl compounds to alpha,beta-unsaturated ketones was reported to be catalyzed by an organic primary amine derived from quinine.
Angewandte Chemie International EditionOrganic‐Catalyst‐Mediated Cyclopropanation Reaction
185 Citations2003Charles D. Papageorgiou, Steven V. Ley +1 more
Angewandte Chemie International EditionAn Intramolecular Organocatalytic Cyclopropanation Reaction
181 Citations2004Nadine Bremeyer, Stephen C. Smith +2 more
The development of a new organocatalytic intramolecular cyclopropanation reaction that forms synthetically versatile bicycloalkanes by using a nucleophilic tertiary amine catalyst is described.
Angewandte Chemie International Edition in EnglishThe Cyclopropyl Group in Studies of Enzyme Mechanism and Inhibition
177 Citations1988Colin J. Suckling
Journal of the American Chemical SocietyExpedient Synthesis of Cyclopropane α-Amino Acids by the Catalytic Asymmetric Cyclopropanation of Alkenes Using Iodonium Ylides Derived from Methyl Nitroacetate
177 Citations2005Benoît Moreau, André B. Charette
1-Nitrocyclopropyl esters are versatile building blocks to access the corresponding cyclopropane amino esters and aminocyclopropanes in two and three steps, respectively, from commercially available products.
ChemInformHighly Enantioselective Michael Addition of Cyclic 1,3‐Dicarbonyl Compounds to α,β‐Unsaturated Ketones.
166 Citations2007Jian‐Wu Xie, Lei Yue +5 more
Organic LettersSubstrate-Directed Stereoselectivity in Vicinal Diamine-Catalyzed Synthesis of Warfarin
166 Citations2006Hyunwoo Kim, Cindy Pai‐Hui Yen +2 more
A new mechanism involving a diimine intermediate is proposed for vicinal diamine-catalyzed synthesis of warfarin by Decreasing the NCCN dihedral angle by varying the diamine results in an increase in the enantioselectivity of warFarin synthesis.
The Journal of Organic ChemistryA Novel Class of Tunable Zinc Reagents (RXZnCH<sub>2</sub>Y) for Efficient Cyclopropanation of Olefins
165 Citations2003Jon C. Lorenz, Jiang Long +4 more
A reasonable level of enantioselectivity was obtained for the cyclopropanation of unfunctionalized olefins when a chiral (iodomethyl)zinc species was used, providing a valuable approach for the asymmetric cyclopromation of uncoupled oleFins.
Journal of the American Chemical SocietyEnhancement of Cyclopropanation Chemistry in the Silver-Catalyzed Reactions of Aryldiazoacetates
156 Citations2007Janelle L. Thompson, Huw M. L. Davies
AgSbF6 is an effective catalyst for the reactions of donor/acceptor substituted carbenoids and shows a very different reactivity profile from the traditional rhodium-catalyzed reactions, notably, cyclopropanation of sterically hindered alkenes is favorable, and products due to a Wolff rearrangement are not observed.
The Journal of Organic ChemistryStereoselective Synthesis of Highly Functionalized Nitrocyclopropanes via Organocatalyic Conjugate Addition to Nitroalkenes
130 Citations2006Séamus H. McCooey, Thomas McCabe +1 more
A convenient and novel one-pot organocatalytic methodology for the stereoselective synthesis of highly functionalized nitrocyclopropanes is reported.
Journal of the American Chemical SocietyControllable Diastereoselective Cyclopropanation. Enantioselective Synthesis of Vinylcyclopropanes via Chiral Telluronium Ylides
120 Citations2003Wei‐Wei Liao, Kai Li +1 more
Either one of the two diastereomers could be enantioselectively synthesized at will just by the choice of LiTMP/HMPA or LDA/LiBr.
The Journal of Organic ChemistryTetrazolic Acid Functionalized Dihydroindol: Rational Design of a Highly Selective Cyclopropanation Organocatalyst
106 Citations2007Antti Hartikka, Per I. Arvidsson
The improved catalyst (S)-(-)-indoline-2-yl-1H-tetrazole provides the best results so far reported for intermolecular enantioselective organocatalyzed cyclopropanation.
Tetrahedron LettersAsymmetric cyclopropanation reaction Under phase-transfer catalyzed conditions
97 Citations1999Shigeru Arai, Keiji Nakayama +2 more
Organic LettersCatalytic Asymmetric Simmons−Smith Cyclopropanation of Silyl Enol Ethers. Efficient Synthesis of Optically Active Cyclopropanol Derivatives
94 Citations2006Haifeng Du, Jiang Long +1 more
A catalytic asymmetric Simmons-Smith cyclopropanation of silyl enol ethers using dipeptide 2 as the ligand and up to 96% ee was obtained.
Tetrahedron LettersOrganocatalytic asymmetric nitrocyclopropanation of α,β-unsaturated aldehydes
94 Citations2008Ján Veselý, Gui‐Ling Zhao +2 more
Journal of the American Chemical SocietyAsymmetric Simmons−Smith Cyclopropanation of Unfunctionalized Olefins
92 Citations2003Jiang Long, Yi Yuan +1 more
This paper describes a promising asymmetric cyclopropanation system for unfunctionalized olefins using readily available dipeptide N-Boc-l-Val- l-Pro-OMe as ligand.
Chemical CommunicationsA new asymmetric organocatalytic nitrocyclopropanation reaction
85 Citations2006Henriette M. Hansen, Deborah A. Longbottom +1 more
Using 5-(pyrrolidin-2-yl)-1H-tetrazole as an organic catalyst, the nitrocyclopropanation of 2-cyclohexen-1-one has been achieved, proceeding in high yield and with good enantioselective control.
Journal of the American Chemical SocietyVinyldiazolactone as a Vinylcarbene Precursor: Highly Selective C−H Insertion and Cyclopropanation Reactions
77 Citations2006Darren Bykowski, Kou-Hui Wu +1 more
The vinyldiazolactone precursor to the metal vinylcarbene possesses superior stability in comparison to previously known vinyLDiazoacetates and, for the first time, allows the use of Z-vinylcarbenes in asymmetric C-H insertion and cyclopropanation reactions.
SynlettDual Catalyst Control in the Chiral Diamine-Dipeptide-Catalyzed Asymmetric Michael Addition
74 Citations2004Svetlana B. Tsogoeva, Sunil B. Jagtap
Angewandte ChemieEnantioselective Organocatalytic Cyclopropanation via Ammonium Ylides
72 Citations2004Charles D. Papageorgiou, Maria A. Cubillo de Dios +2 more
Angewandte ChemieFaszinierende natürliche und synthetische Cyclopropan-Architekturen
59 Citations2001Rüdiger Faust
Tetrahedron LettersAsymmetric synthesis of activated cyclopropanes catalyzed by cinchonidine as a chiral Brønsted base
54 Citations2006Satoshi Kojima, Maki Suzuki +2 more
Angewandte Chemie International EditionDiastereoselective Synthesis of Methylenecyclopropanes from Chiral Cyclopropene Derivatives
53 Citations2006Zhe Yang, Xiaocong Xie +1 more
Angewandte ChemieEnantioselective Catalytic Intramolecular Cyclopropanation using Modified Cinchona Alkaloid Organocatalysts
52 Citations2006Carin C. C. Johansson, Nadine Bremeyer +4 more
The Journal of Organic ChemistryStereoselective Synthesis of Cyclopropane Rings under Phase-Transfer-Catalyzed Conditions
50 Citations1998Shigeru Arai, Keiji Nakayama +2 more
Chemistry - A European JournalFinal Elucidation of the Absolute Configuration of the Signal Metabolite Hormaomycin
47 Citations2004Boris D. Zlatopolskiy, Karin V. Loscha +5 more
The complete absolute configuration of hormaomycin 1 a has been established by HPLC and HPLC/MS experiments with appropriately derivatized 4-propylprolines, (2S,4S)-6 and (2R,4R)-6, as well as 4-(Z)-propenylpro lines, cis-5 and trans-5.
Angewandte ChemieAn Intramolecular Organocatalytic Cyclopropanation Reaction
46 Citations2004Nadine Bremeyer, Stephen C. Smith +2 more
Angewandte ChemieDie Cyclopropylgruppe in Untersuchungen über Mechanismus und Hemmung von Enzymen
42 Citations1988Colin J. Suckling
Organic LettersHighly Diastereoselective Simmons−Smith Cyclopropanation of Allylic Amines
37 Citations2003Varinder K. Aggarwal, Guang Yu Fang +1 more
Cyclopropanation of allylic tertiary amines using the Simmons-Smith reagent has been achieved by employing chelating groups in close proximity to the amine at the expense of N-ylide formation.
SynlettA General Procedure for theOne-pot Preparation of Polyfunctionalized Nitrocyclopropanes
29 Citations2003Roberto Ballini, Dennis Fiorini +1 more
Angewandte ChemieOrganic‐Catalyst‐Mediated Cyclopropanation Reaction
27 Citations2003Charles D. Papageorgiou, Steven V. Ley +1 more
Angewandte Chemie International EditionEnantioselective Synthesis of Cyclopropanes by Aldehyde Homologation
24 Citations2004Christina A. Risatti, Richard E. Taylor
Angewandte ChemieDiastereoselective Synthesis of Methylenecyclopropanes from Chiral Cyclopropene Derivatives
16 Citations2006Zhe Yang, Xiaocong Xie +1 more
Angewandte ChemieEnantioselective Synthesis of Cyclopropanes by Aldehyde Homologation
7 Citations2004Christina A. Risatti, Richard E. Taylor