Intermolecular Asymmetric Carboesterification of Alkenes by Using Chiral Amine Auxiliaries under O<sub>2</sub>: Synthesis of Enantioenriched α‐Methylene‐γ‐Lactones through Chloropalladation of Alkynes

Zhang, Zhenming; Wu, Wanqing; Liao, Jianhua; Li, Jianxiao; Jiang, Huanfeng

doi:10.1002/chem.201500397

Cited by 24 publications

(13 citation statements)

References 93 publications

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“…The asymmetric synthesis of amines attracts significant attention due to their multiple immediate applications and versatility as building blocks in the preparation of bioactive molecules . In addition, amines have been widely employed as chiral auxiliaries, asymmetric catalysts, and chiral resolving agents …”

Section: Introductionmentioning

confidence: 92%

Biocatalytic Transamination for the Asymmetric Synthesis of Pyridylalkylamines. Structural and Activity Features in the Reactivity of Transaminases

et al. 2016

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ABSTRACT. A set of transaminases has been investigated for the biocatalytic amination of 1-(4-chloropyridin-2-yl)alkan-1-ones. The influence of the chain length of the n-1-alkanone at the C-2 position of the pyridine has been studied in the reaction with different (R)-and (S)-selective transaminases. Thus, enantiopure amines were isolated with high purity starting from a wide selection of prochiral ketones. On the one hand excellent yields (97->99% conversion, up to 93% isolated yield) and stereoselectivity values (>99% ee for both amine enantiomers) were found for n-1-alkanone linear short chain substituents such as ethanone or propanone. On the other hand, more hindered substrates were accepted only when using evolved enzymes such as an evolved variant of (R)-Arthrobacter (ArRmut11-TA). An initial common structural feature was the presence of a chlorine atom on the C-4 position of the pyridine core, which was found to increase the reactivity of the starting ketone, giving extra versatility for the introduction of other chemical functionalities towards more complex and applicable organic molecules. In order to gain a deeper understanding about the substrate specificity of different transaminases, additional structural features were considered by variation of the acetyl group position on the pyridine ring and the use of related acetophenone derivatives.

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Section: Introductionmentioning

confidence: 92%

Biocatalytic Transamination for the Asymmetric Synthesis of Pyridylalkylamines. Structural and Activity Features in the Reactivity of Transaminases

et al. 2016

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“…The same authors reported an asymmetric variant to this transformation using a chiral amine auxiliary in 2015 (Scheme 221a). 385 This method allowed efficient access to a wide variety of chiral α-methylene-γ-lactones 312 with high levels of E:Z selectivity. During the optimization process the authors found (1S,2S)-N,N-dimethylcyclohexane-1,2-diamine was the optimal source of chirality.…”

Section: Carbohalogenation Of Alkynes By Halometalationmentioning

confidence: 99%

“…The same authors reported an asymmetric variant to this transformation using a chiral amine auxiliary in 2015 (Scheme a) . This method allowed efficient access to a wide variety of chiral α-methylene-γ-lactones 312 with high levels of E:Z selectivity.…”

Section: Synthesis Of Vinyl Halidesmentioning

confidence: 99%

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

2016

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The high utility of halogenated organic compounds has prompted the development of a vast number of transformations which install the carbon-halogen motif. Traditional routes to these building blocks have commonly involved multiple steps, harsh reaction conditions, and the use of stoichiometric and/or toxic reagents. In this regard, using transition metals to catalyze the synthesis of organohalides has become a mature field in itself, and applying these technologies has allowed for a decrease in the production of waste, higher levels of regio- and stereoselectivity, and the ability to produce enantioenriched target compounds. Furthermore, transition metals offer the distinct advantage of possessing a diverse spectrum of mechanistic possibilities which translate to the capability to apply new substrate classes and afford novel and difficult-to-access structures. This Review provides comprehensive coverage of modern transition metal-catalyzed syntheses of organohalides via a diverse array of mechanisms. Attention is given to the seminal stoichiometric organometallic studies which led to the corresponding catalytic processes being realized. By breaking this field down into the synthesis of aryl, vinyl, and alkyl halides, it becomes clear which methods have surfaced as most favored for each individual class. In general, a pronounced shift toward the use of C-H bonds as key functional groups, in addition to methods which proceed by catalytic, radical-based mechanisms has occurred. Although always evolving, this field appears to be heading in the direction of using starting materials with a significantly lower degree of prefunctionalization in addition to less expensive and abundant metal catalysts.

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“…and subsequent transition-metal-catalyzed strategies have been developed. Vinyl chlorides were commonly constructed by hydrohalogenation of alkynes, carbohalogenation of alkynes, and other reaction types . For the synthesis of alkyl chlorides, transition-metal-catalyzed cross-coupling reactions have recently become synthetically useful through high valent metal centers.…”

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confidence: 99%

Intermolecular Asymmetric Carboesterification of Alkenes by Using Chiral Amine Auxiliaries under O₂: Synthesis of Enantioenriched α‐Methylene‐γ‐Lactones through Chloropalladation of Alkynes

Cited by 24 publications

References 93 publications

Biocatalytic Transamination for the Asymmetric Synthesis of Pyridylalkylamines. Structural and Activity Features in the Reactivity of Transaminases

Biocatalytic Transamination for the Asymmetric Synthesis of Pyridylalkylamines. Structural and Activity Features in the Reactivity of Transaminases

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

Palladium-Catalyzed Nitrile-Assisted C(sp³)–Cl Bond Formation for Synthesis of Dichlorides

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Intermolecular Asymmetric Carboesterification of Alkenes by Using Chiral Amine Auxiliaries under O2: Synthesis of Enantioenriched α‐Methylene‐γ‐Lactones through Chloropalladation of Alkynes

Cited by 24 publications

References 93 publications

Biocatalytic Transamination for the Asymmetric Synthesis of Pyridylalkylamines. Structural and Activity Features in the Reactivity of Transaminases

Biocatalytic Transamination for the Asymmetric Synthesis of Pyridylalkylamines. Structural and Activity Features in the Reactivity of Transaminases

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

Palladium-Catalyzed Nitrile-Assisted C(sp3)–Cl Bond Formation for Synthesis of Dichlorides

Contact Info

Product

Resources

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Intermolecular Asymmetric Carboesterification of Alkenes by Using Chiral Amine Auxiliaries under O₂: Synthesis of Enantioenriched α‐Methylene‐γ‐Lactones through Chloropalladation of Alkynes

Palladium-Catalyzed Nitrile-Assisted C(sp³)–Cl Bond Formation for Synthesis of Dichlorides