Cinchona Alkaloid-Catalyzed Enantioselective Monofluoromethylation Reaction Based on Fluorobis(phenylsulfonyl)methane Chemistry Combined with a Mannich-type Reaction

Mizuta, Satoshi; Shibata, Norio; Goto, Yasumasa; Furukawa, Tatsuya; Nakamura, Shuichi; Toru, Takeshi

doi:10.1021/ja071509y

Cited by 171 publications

(68 citation statements)

References 22 publications

(9 reference statements)

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“…[16] The role of the base in the coupling reaction remains unclear at present. Conceivably, the additives remove halide ions or BA C H T U N G T R E N N U N G (OMe) 3 , which is formed as a by-product and which we found to inhibit the reaction. [17] We briefly investigated the influence of the halogen leaving group on the cross-coupling reaction.…”

mentioning

confidence: 81%

Synthesis of Trifluorostyrene Derivatives by Palladium‐Catalyzed Cross‐Coupling of Lithium Trimethoxy(trifluorovinyl)borate with Aryl Bromides

Duric

Schmidt

Ninnemann

et al. 2011

Chemistry A European J

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mentioning

confidence: 81%

Synthesis of Trifluorostyrene Derivatives by Palladium‐Catalyzed Cross‐Coupling of Lithium Trimethoxy(trifluorovinyl)borate with Aryl Bromides

Duric

Schmidt

Ninnemann

et al. 2011

Chemistry A European J

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“…[121] Die gleiche Synthesestrategie nutzten Shibata und Toru et al für eine hoch enantioselektive Monofluormethylierung mit 1-Fluorbis(phenylsulfonyl)methan und dem Katalysator 1 o (Schema 93). [122] Des Weiteren sind hoch enantioselektive Mannich-Reaktionen von a-substituierten Cyansulfonen wie 153 [123] und 3-substituierten Oxindolen, z. B.…”

Section: Ma Et Al Berichteten üBer Die Hoch Enantioselektiveunclassified

Neue Entwicklungen bei asymmetrischen Phasentransferreaktionen

2013

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Die Phasentransferkatalyse bildet eine effiziente Grundlage zur Einführung praktischer Methoden in die organische Synthese, denn sie bietet mehrere Vorteile wie einfache Handhabung, milde Reaktionsbedingungen, die Eignung für großtechnische Synthesen und ein umweltfreundliches Reaktionssystem. Seit den wegweisenden Arbeiten zu hoch enantioselektiven Alkylierungen mit chiralen Phasentransferkatalysatoren ist dieses Forschungsgebiet im Hinblick auf eine umweltverträgliche, nachhaltige Chemie von Interesse, und in den vergangenen Jahrzehnten, vor allem in den letzten Jahren, wurden zahlreiche asymmetrische, durch chirale Oniumsalze und Kronenether katalysierte Umwandlungen für die Synthese wertvoller organischer Verbindungen entwickelt.

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“…[1][2][3] Although more advanced, direct methods capable of merging steps (1) and (2) by means of catalytic activation of the substrates still remain challenging. To date, sulfone-based direct catalytic C-C bond-forming methods are confined to either a-fluoro bis(phenylsulfonyl)methane [4] or monosulfones bearing an additional carbonyl, ester, or nitrile group at the a-position (Scheme 1). [5] Here we describe the first general catalytic,…”

Section: Introductionmentioning

confidence: 99%

Catalytic Conjugate Additions of Geminal Bis(sulfone)s: Expanding the Chemistry of Sulfones as Simple Alkyl Anion Equivalents

Landa

Puente

Santos

et al. 2009

Chemistry A European J

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The value of cyclic gem-bis(sulfone) 4 as a simple alkyl nucleophile equivalent in catalytic C-C bond-forming reactions is demonstrated. The 1,4-type nucleophilic additions of bis(sulfone) 4 to alpha,beta-unsaturated ketones take place by assistance of catalytic guanidine base. On the other hand, pyrrolidines are able to catalyze the conjugate addition of 4 to both enones and enals, likely by means of iminium ion activation. Upon exploration of the best chiral pyrrolidine catalyst, it has been found that the addition of 4 to enals catalyzed by diphenylprolinol silyl ether 10 proceeds with very high enantioselectivity (beta-aryl-substituted enals >95% ee; beta-alkyl substituted enals up to 94% ee; ee = enantiomeric excess). Further reductive desulfonation of adducts gives rise to the corresponding beta-methyl aldehydes, as well as the derived alcohols, acetals, and methyl esters after simple (Mg, MeOH) well-established protocols. Application of the procedure to the synthesis of biologically relevant phenethyl building blocks is shown. Most interestingly, alpha-alkylation of initially obtained bis(sulfone) adducts can be done even with less reactive alkylating reagents, such as long linear-chain or branched-chain alkyl halides. Accordingly, upon the desulfonation process, a general, experimentally simple and highly enantioselective access to beta-branched aldehydes, alcohols, or esters is possible. Further exploration of the method includes the use of chiral alpha,beta-unsaturated aldehydes derived from citronellal as the Michael acceptor partners. In these instances, the sense of the conjugate addition of 4 is controlled by the chirality of the pyrrolidine catalyst, thus allowing for a stereochemically predictable access to 1,3-dimethyl arrays, such as those present in deoxygenated polyketide-type natural products. The intramolecular variation of this technology by using doubly unsaturated aldehyde-ester 22 illustrated the site selectivity of the procedure and its potential for tandem processes leading to highly substituted polycyclic systems, such as 24.

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Cinchona Alkaloid-Catalyzed Enantioselective Monofluoromethylation Reaction Based on Fluorobis(phenylsulfonyl)methane Chemistry Combined with a Mannich-type Reaction

Cited by 171 publications

References 22 publications

Synthesis of Trifluorostyrene Derivatives by Palladium‐Catalyzed Cross‐Coupling of Lithium Trimethoxy(trifluorovinyl)borate with Aryl Bromides

Synthesis of Trifluorostyrene Derivatives by Palladium‐Catalyzed Cross‐Coupling of Lithium Trimethoxy(trifluorovinyl)borate with Aryl Bromides

Neue Entwicklungen bei asymmetrischen Phasentransferreaktionen

Catalytic Conjugate Additions of Geminal Bis(sulfone)s: Expanding the Chemistry of Sulfones as Simple Alkyl Anion Equivalents

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