Cu-Catalyzed S<sub>N</sub>2′ Substitution of Propargylic Phosphates with Vinylarene-Derived Chiral Nucleophiles: Synthesis of Chiral Allenes

Wang, Bing; Wang, Xihong; Yin, Xiufeng; Yu, Wangzhi; Liao, Yang; Ye, Jialin; Wang, Min; Liao, Jian

doi:10.1021/acs.orglett.9b00908

Cited by 28 publications

(9 citation statements)

References 90 publications

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“…Both Yun and Liao recently expanded these reactions by using propargylic phosphates to access the allene-based products (Scheme ). While Yun’s catalytic system targeted aryl-substituted allenes ( 105 ) and Liao’s work focused on alkyl-substituted allenes ( 106 ), both products were obtained in high enantioselectivity illustrating a powerful method toward chiral allenes.…”

Section: Allylation/propargylationmentioning

confidence: 99%

Copper-Catalyzed Borylative Difunctionalization of π-Systems

et al. 2020

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Organoboronates represent a cornerstone functional group in modern synthesis owing to their unique reactivity and divergent synthetic capability. Copper catalysis has become one of the most powerful methods to stereoselectively install boron across diverse π-systems. Additionally, this method affords tremendous versatility enabled by difunctionalization of the π-system by the addition of an electrophile. This review covers known electrophiles to intercept catalytic intermediates in borylative difunctionalization strategies that have been reported up to the end of May 2020.

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Section: Allylation/propargylationmentioning

confidence: 99%

Copper-Catalyzed Borylative Difunctionalization of π-Systems

et al. 2020

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“…Allyl, benzyl and propargyl phosphates were synthesized from the corresponding alcohols as reported in the literature. 49–52 Thiosilane ( 2b–2d ) was synthesized from the corresponding thiols as reported in the literature. 31…”

Section: Methodsmentioning

confidence: 99%

Gold-catalyzed thioetherification of allyl, benzyl, and propargyl phosphates

Miura

Toyomasu

Nishio

et al. 2022

Catal. Sci. Technol.

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“…But-2-yn-1-ol was commercially available and used as received. 1,2,3,4-Tetra-Oacetyl-β-D-xylopyranose 7, 11b 3-(4-fluorophenyl)prop-2-yn-1-ol, 25 and 4,4-dimethylpent-2-yn-1-ol 26 were synthesized as previously described in the literature. NMR measurements were obtained using a Bruker Avance I spectrometer equipped with a QNP probe (250 MHz for the 1 H), a Bruker Avance III spectrometer equipped with a BBFO + probe (500 MHz for 1 H, 126 MHz for 13 C, and 471 MHz for 19 F), or a Bruker AVANCE III spectrometer equipped with a CPTCI Cryosonde (600 MHz for 1 H and 151 MHz for 13 C).…”

Section: ■ Conclusionmentioning

confidence: 99%

Diastereoselective Synthesis of Axially Chiral Xylose-Derived 1,3-Disubstituted Alkoxyallenes: Scope, Structure, and Mechanism

et al. 2020

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The deprotonation of differently substituted propargyl xylosides with s-BuLi/TMEDA followed by protonation with t-butanol at-115 °C provided a range of new axially chiral 1,3-disubstituted alkoxyallenes in a diastereoselective way. Numerous reaction parameters such as solvent, temperature or protonating agent were examined as well as protecting groups on the xyloside moiety and the influence of the substituents on the alkyne part. The configuration of the main diastereoisomer of 3-methyl-1-xyloside-allene was determined for the first time by single crystal X-ray diffraction analysis and nOe NMR experiments. Furthermore, DFT calculations on the propargyl/allenyl lithium intermediates formed in the course of the deprotonation reaction provided new structural insights of these complexes. The subsequent protonation process with alcohols was investigated by theoretical surface exploration, revealing the importance of the approach of the alcohol towards the lithium compounds on the reaction outcome. Results and Discussion Synthesis of various substituted propargyl xylosides 3a-f from 1. Propargyl β-D-xylopyranoside 1 can be obtained either by a classical three-step chemical sequence from D-xylose or through an enzymatic transglycosylation process directly from beechwood xylans and propargyl alcohol. 6c,11 The fully TBS protected propargyl xyloside 2 was readily prepared in up to 91 % yield from 1 by reaction with t-butyldimethylsilyl chloride (TBS-Cl) in presence of imidazole and a catalytic amount of DMAP (Scheme 3) after heating at 80 °C for 6 days. 5b Lower temperatures or shorter reaction times led to the formation of product mixtures containing diand triprotected xylosides. Introduction of substituents on the alkyne was carried out via deprotonation and nucleophilic substitution for alkyl or silyl groups leading to 3a,b or Pd-catalyzed Sonogashira 12 coupling for aryl groups providing 3c-e in good to excellent yields. The t-butyl substituted compound 3f could not be obtained by these pathways, but via a 4-step procedure from D-xylose (see S1 in SI). Scheme 3. Synthesis of various propargyl xylosides 2 and 3a-e.

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Cu-Catalyzed S_N2′ Substitution of Propargylic Phosphates with Vinylarene-Derived Chiral Nucleophiles: Synthesis of Chiral Allenes

Cited by 28 publications

References 90 publications

Copper-Catalyzed Borylative Difunctionalization of π-Systems

Copper-Catalyzed Borylative Difunctionalization of π-Systems

Gold-catalyzed thioetherification of allyl, benzyl, and propargyl phosphates

Diastereoselective Synthesis of Axially Chiral Xylose-Derived 1,3-Disubstituted Alkoxyallenes: Scope, Structure, and Mechanism

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Cu-Catalyzed SN2′ Substitution of Propargylic Phosphates with Vinylarene-Derived Chiral Nucleophiles: Synthesis of Chiral Allenes

Cited by 28 publications

References 90 publications

Copper-Catalyzed Borylative Difunctionalization of π-Systems

Copper-Catalyzed Borylative Difunctionalization of π-Systems

Gold-catalyzed thioetherification of allyl, benzyl, and propargyl phosphates

Diastereoselective Synthesis of Axially Chiral Xylose-Derived 1,3-Disubstituted Alkoxyallenes: Scope, Structure, and Mechanism

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Cu-Catalyzed S_N2′ Substitution of Propargylic Phosphates with Vinylarene-Derived Chiral Nucleophiles: Synthesis of Chiral Allenes