Synthesis and Reactions of Allylic, Allenic, Vinylic, and Arylmetal Reagents from Halides and Esters via Transient Organopalladium Intermediates

Marshall, James A.

doi:10.1021/cr000003u

Cited by 450 publications

(144 citation statements)

References 55 publications

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“…155a, 159 The reaction of an in situ generated chiral allenylzinc reagent with various aldehydes afforded homopropargylic alcohols of high enantiomeric purity (Scheme 61). 160 Additions of the chiral allenylzinc to α-methyl-or silyloxysubstituted aldehydes were highly diastereoselective favoring the anti isomer with negligible mismatching.…”

Section: Scheme 59mentioning

confidence: 99%

Diastereoselective Allylation of Carbonyl Compounds and Imines: Application to the Synthesis of Natural Products

2013

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2.2. Chiral Imines and Imine Derivatives 2.2.1. Imines and Imine Derivatives from Chiral Carbonyl Compounds. Chiral α-oxysubstituted aldehydes were used by Kobayashi and co-workers in a three-component reaction with allylboropinacolate and ammonia in ethanol. The corresponding homoallylic primary amines were obtained with good to high syn diastereofacial selectivities (Scheme 5). 20 The precise reaction mechanism was unclear. Preformation of N-Scheme 3 Scheme 4 Scheme 5 Chemical Reviews Review dx.

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Section: Scheme 59mentioning

confidence: 99%

Diastereoselective Allylation of Carbonyl Compounds and Imines: Application to the Synthesis of Natural Products

2013

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“…One way to address these issues would be to use the Marshall procedure, whereby a chain elongation is achieved through the addition of a chiral allene to an aldehyde. [9,10] In order to compliment the crotylation protocol, we have therefore developed a flow process for the boron trifluoride etherate mediated homopropargylation under Marshall conditions. [10] In a series of optimisation reactions, we found that the flow process allowed for a significant reduction in the amount of toxic stannane needed to obtain comparable yields to the corresponding batch processes.…”

Section: Reduction In Flowmentioning

confidence: 99%

Diastereoselective Chain‐Elongation Reactions Using Microreactors for Applications in Complex Molecule Assembly

Carter

Lange

Sakai

et al. 2011

Chemistry A European J

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Diastereoselective chain-elongation reactions are important transformations for the assembly of complex molecular structures, such as those present in polyketide natural products. Here we report new methods for performing crotylation reactions and homopropargylation reactions by using newly developed low-temperature flow-chemistry technology. In-line purification protocols are described, as well as the application of the crotylation protocol in an automated multi-step sequence.

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“…[41][42][43] Furthermore, of the large number of natural products containing an allene moiety that have been isolated, most have axial chirality. 44) For these reasons, extensive studies on the synthesis of allenes have been undertaken, [41][42][43] and the S N 2′-type substitution reaction of propargylic oxiranes with organometallic reagents has emerged as one of the most successful procedures to afford 2,3-allenols. 45) Propargylic oxiranes generally react with organocopper, 46) magnesium 47) and metal hydride 48) to produce the substituted 2,3-allenols in moderate to high diastereoselectivity.…”

Section: Diastereoselective Construction Of Substituted 23-allenols mentioning

confidence: 99%

Development of Palladium-Catalyzed Transformations Using Propargylic Compounds

Yoshida

2012

CHEMICAL & PHARMACEUTICAL BULLETIN

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It is known that propargylic compounds having an ester and a halide at the propargylic positions react with palladium complexes leading to π-propargylpalladium and allenylpalladium complexes, which cause various transformations in the presence of the reactants. The aim of the present study was to develop novel palladium-catalyzed transformations using propargylic compounds. As diastereoselective reactions of propargylic compounds with bis-nucleophiles, we have developed palladium-catalyzed reactions of propargylic carbonates with 2-substituted cyclohexane-1,3-diones, 2-(2-hydroxyphenyl)acetates and 2-oxocyclohex-3-enecarboxylates. These processes produce highly substituted cyclic compounds in a highly stereoselective manner. Through our studies on the construction of substituted 2,3-allenols by the reactions of propargylic oxiranes, it has been made clear that palladium-catalyzed coupling reactions occur in the presence of arylboronic acids and terminal alkynes. The processes can be carried out in mild conditions to yield substituted 4-aryl-2,3-allenols in a diastereoselective manner. In our attempt to develop CO 2 -recycling reactions, we developed a methodology for the synthesis of cyclic carbonates by palladium-catalyzed reactions of propargylic carbonates with phenols. Our findings suggested that the process proceeds through a pathway involving decarboxylation-followed fixation of the liberated CO 2 . Diastereoselective, enantioselective, and enantiospecific construction of cyclic carbonates have been achieved by the application of this methodology.

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Synthesis and Reactions of Allylic, Allenic, Vinylic, and Arylmetal Reagents from Halides and Esters via Transient Organopalladium Intermediates

Cited by 450 publications

References 55 publications

Diastereoselective Allylation of Carbonyl Compounds and Imines: Application to the Synthesis of Natural Products

Diastereoselective Allylation of Carbonyl Compounds and Imines: Application to the Synthesis of Natural Products

Diastereoselective Chain‐Elongation Reactions Using Microreactors for Applications in Complex Molecule Assembly

Development of Palladium-Catalyzed Transformations Using Propargylic Compounds

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