Catalytic stereodivergent total synthesis of amathaspiramide D

He, Zhuozhuo; Peng, Lingzi; Guo, Chang

doi:10.1038/s44160-022-00063-y

Cited by 60 publications

(33 citation statements)

References 47 publications

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“…Among those reactions, the nickel-catalyzed asymmetric propargylation is an important strategy for the construction of optically active alkyne compounds 49 – 58 . Especially, the chiral Ni/Cu dual catalyzed asymmetric α−propargylation of aldimine esters reported by Guo et al provided a good solution for the preparation of chiral propargyl-functionalized amino acids 59 , 60 , a type of useful compound that has been seldom studied by synthetic chemists (Fig. 1b ) 61 – 65 .…”

Section: Introductionmentioning

confidence: 99%

Chiral aldehyde-nickel dual catalysis enables asymmetric α−propargylation of amino acids and stereodivergent synthesis of NP25302

Zhu

et al. 2022

Nat Commun

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The combined catalytic systems derived from organocatalysts and transition metals exhibit powerful activation and stereoselective-control abilities in asymmetric catalysis. This work describes a highly efficient chiral aldehyde-nickel dual catalytic system and its application for the direct asymmetric α−propargylation reaction of amino acid esters with propargylic alcohol derivatives. Various structural diversity α,α−disubstituted non-proteinogenic α−amino acid esters are produced in good-to-excellent yields and enantioselectivities. Furthermore, a stereodivergent synthesis of natural product NP25302 is achieved, and a reasonable reaction mechanism is proposed to illustrate the observed stereoselectivity based on the results of control experiments, nonlinear effect investigation, and HRMS detection.

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Section: Introductionmentioning

confidence: 99%

Chiral aldehyde-nickel dual catalysis enables asymmetric α−propargylation of amino acids and stereodivergent synthesis of NP25302

Zhu

et al. 2022

Nat Commun

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“…[36b] Subsequently, an elegant procedure for stereodivergent propargylic substitution that provides four diastereoisomers of amathaspiramide D was reported by the same group (Scheme 16). [37] Based on their previous studies on Ni/Cucatalyzed propargylic substitution, the reaction of substituted propargylic carbonate with aldimine esters has been realized for the synthesis of products bearing two vicinal stereocenters. The results are excellent (up to 76 % yield, > 20 : 1 dr, and > 99 % ee).…”

Section: Kurzaufsätzementioning

confidence: 99%

Bimetallic Catalysis in Stereodivergent Synthesis

Huo

Wang

et al. 2022

Angewandte Chemie

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Bimetallic catalysis has emerged as an efficient strategy for the development of new chemical reactions. Importantly, this strategy also provides a simple and powerful platform for stereodivergent synthesis, whereby all the possible stereoisomers of products bearing two stereocenters can be easily prepared from the same set of starting materials. In this Minireview, the development of stereodivergent allylic substitution, propargylic substitution, hydrofunctionalization, and annulation based on bimetallic catalysis has been summarized. It is expected that more bimetallic catalytic systems will be developed and applied for the stereodivergent synthesis of valuable molecules.

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“…Transition-metal-catalyzed asymmetric propargylic substitution (APS) reactions have been utilized extensively for designing and manipulating molecular structures to increase the skeletal diversity and complexity of molecules in fields such as total synthesis, medicine, and materials science (Scheme C) . Since the pioneering study by Tsuji and Kawatsura, significant effort has been devoted to nickel-catalyzed APS reactions with excellent levels of enantiocontrol for introducing the internal alkyne functionality.…”

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confidence: 99%

Nickel-Catalyzed Asymmetric Propargylation for the Synthesis of Axially Chiral 1,3-Disubstituted Allenes

Wang

Peng

et al. 2022

J. Am. Chem. Soc.

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The general enantioselective catalytic synthesis of axially chiral 1,3-disubstituted allenes from readily available racemic propargylic alcohol derivatives remains a long-standing challenge in organic synthesis. Here we report an efficient nickel-catalyzed asymmetric propargylic substitution reaction/Myers rearrangement of racemic propargylic carbonates that furnishes a series of enantioenriched 1,3-disubstituted allenes using newly designed N-sulfonylhydrazone reagents as efficient diazo surrogates. This reaction proved to be remarkably general with regard to substrate scope, affording a diverse range of 1,3-disubstituted allenic compounds in good yields with excellent enantioselectivities. Additionally, applications of this powerful strategy for the enantioselective synthesis of methyl (S)-8-hydroxyocta-5,6-dienoate, (S)-laballenic acid, (S)-phlomic acid, and (S)-Δ9,10-pentacosadiene are described, further highlighting the broad potential of these new reagents for the discovery of novel reactions.

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Catalytic stereodivergent total synthesis of amathaspiramide D

Cited by 60 publications

References 47 publications

Chiral aldehyde-nickel dual catalysis enables asymmetric α−propargylation of amino acids and stereodivergent synthesis of NP25302

Chiral aldehyde-nickel dual catalysis enables asymmetric α−propargylation of amino acids and stereodivergent synthesis of NP25302

Bimetallic Catalysis in Stereodivergent Synthesis

Nickel-Catalyzed Asymmetric Propargylation for the Synthesis of Axially Chiral 1,3-Disubstituted Allenes

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