Phosphine-Mediated Olefination between Aldehydes and Allenes: An Efficient Synthesis of Trisubstituted 1,3-Dienes with High <i>E</i>-Selectivity

Xu, Silong; Zhou, Lun; Zeng, San; Ma, Renqin; Wang, Zhihong; He, Zhengjie

doi:10.1021/ol901334c

Cited by 58 publications

(12 citation statements)

References 53 publications

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“…They demonstrated that triphenylphosphine could be used as the catalyst to isomerize γ -benzyl allenoate to the corresponding 2,4-dienoate in good yield. 179 Mechanistically, the initial addition of the phosphine occurs at the β -position of the γ -benzyl allenoate, resulting in the formation of the phosphonium dienolate 71 . After proton transfer, the vinylogous phosphonium ylide 72 is formed.…”

Section: Nucleophilic Phosphine Catalysis Of Allenesmentioning

confidence: 99%

“…In 2009, He and co-workers employed tertiary phosphines to promote internal ylide generation from γ -substituted allenoates (Scheme 672). 179 Employing the phosphonium ylide generated from nucleophilic addition of the phosphine to the allenoate, various functionalized diene systems were formed, exclusively with the E , E -configuration.…”

Section: Ylides Formed Through Nucleophilic Addition Of Phosphinementioning

confidence: 99%

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Phosphine Organocatalysis

et al. 2018

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The hallmark of nucleophilic phosphine catalysis is the initial nucleophilic addition of a phosphine to an electrophilic starting material, producing a reactive zwitterionic intermediate, generally under mild conditions. In this Review, we classify nucleophilic phosphine catalysis reactions in terms of their electrophilic components. In the majority of cases, these electrophiles possess carbon–carbon multiple bonds: alkenes (section 2), allenes (section 3), alkynes (section 4), and Morita–Baylis–Hillman (MBH) alcohol derivatives (MBHADs; section 5). Within each of these sections, the reactions are compiled based on the nature of the second starting material—nucleophiles, dinucleophiles, electrophiles, and electrophile–nucleophiles. Nucleophilic phosphine catalysis reactions that occur via the initial addition to starting materials that do not possess carbon–carbon multiple bonds are collated in section 6. Although not catalytic in the phosphine, the formation of ylides through the nucleophilic addition of phosphines to carbon–carbon multiple bond–containing compounds is intimately related to the catalysis and is discussed in section 7. Finally, section 8 compiles miscellaneous topics, including annulations of the Hüisgen zwitterion, phosphine-mediated reductions, iminophosphorane organocatalysis, and catalytic variants of classical phosphine oxide–generating reactions.

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Section: Nucleophilic Phosphine Catalysis Of Allenesmentioning

confidence: 99%

Section: Ylides Formed Through Nucleophilic Addition Of Phosphinementioning

confidence: 99%

Phosphine Organocatalysis

et al. 2018

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“…7b,c,f The pioneering work by He and other researchers has demonstrated that allenoates and alkynoates also possess decent reactivity in stoichiometric phosphine-mediated olefination reactions with carbonyls. 18 In 2009, He and co-workers 19 disclosed a novel olefination reaction between c-substituted allenoates 19 and aldehydes under the mediation of phosphines such as PPh 3 or 1,3,5-triaza-7-phosphaadamantane (PTA), that provided trisubstituted 1,3-dienes 20 in high yields with exclusive E,E-selectivity (Scheme 10, eqn 1). Results indicated that the chemoselectivity was highly dependent on the nature of the c-substituent of the allenoates.…”

Section: Based On Electron-deficient Allene or Alkyne Substratesmentioning

confidence: 99%

Recent advances in stoichiometric phosphine-mediated organic synthetic reactions

2013

RSC Adv.

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Silong Xu a and Zhengjie He* b Organic synthetic reactions mediated by tertiary phosphines have attracted much attention in the organic chemistry community in the past two decades. These reactions can be divided into two categories: phosphine-catalyzed and stoichiometric phosphine-mediated transformations. While the phosphinecatalyzed reactions mechanistically rely on the unique properties of tertiary phosphines such as excellent nucleophilicity and good leaving group ability, the stoichiometric transformations are usually driven by nucleophilicity and strong oxyphilicity of tertiary phosphines. Since tertiary phosphines represent an important class of versatile chemical reagents in organic synthesis, stoichiometric phosphine-mediated reactions have recently demonstrated their uniqueness and high efficiency in organic synthesis, particularly with respect to the construction of carbon-carbon and carbon-heteroatom bonds, and therefore have stimulated much research interest. In this review, recent advances in stoichiometric phosphine-mediated reactions primarily including olefinations and annulations are summarized.

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“…通过叔膦与亲电性底物原位形成的烯丙基磷叶立德具有丰富的反应性, 相关研究在近年来引起了化学家浓厚的研究兴趣 [14] . 贺峥杰小组 [15] 和 Kwon 小组 [16] 值得一提的是, 与 γ-甲基联烯酸酯不同, γ-苄基或 γ-甲氧羰甲基联烯酸酯与醛或水杨醛反应时, 未能发生叔膦催化的环化反应, 而是经原位形成的烯丙基磷叶立德 17 与醛的 Wittig 反应, 生成多取代共轭二烯烃(Scheme 10) [19,23] . 这种反应性的差异可能源于苯基或酯基的共轭及立体位阻效应, 促使烯丙基磷叶立德 17 主要通过 α 位碳对醛进行亲核进攻, 从而发生经典的 Wittig 反应.…”

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Progress on Vinylogous Organic Reactions of Allylic Phosphorus Ylides with Carbonyl Compounds

Xu¹,

He²

2014

Chin. J. Org. Chem.

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Allylic phosphorus ylides are a class of important and versatile intermediates in synthetic organic chemistry. Due to the delocalization of the carbanion center, an array of vinylogous organic reactions of allylic phosphorus ylides through γ-attack of the carbanion have been achieved in recent years. This mini-review aims to summarize the vinylogous reactivity of allylic phosphorus ylides toward carbonyl compounds, mainly including vinylogous Wittig reactions and various annulation reactions. These reactions broaden the application of allylic phosphorus ylides in organic chemistry, and also provide new synthetic methods for many important organic molecules. Keywords phosphorus ylide; vinylogy; Wittig reaction; annulation reaction Vinylogy 规则 [1] 又名插烯规则, 是指官能团所表现的亲核性或亲电性能够通过一个或多个乙烯单元进行传递而导致反应位点发生改变的现象. 从现代化学角度来看, vinylogy 规则可用共轭效应的极性交替分布原理来解释 [2]. vinylogy 规则在许多重要的碳碳键形成反应中得到运用, 如 Aldol 反应 [3] 、Mannich 反应 [4] 、Morita-Baylis-Hillman 反应 [5] 等. 这一规则的运用显著拓展了这些重要反应的底物适应范围, 丰富了相关反应在有机合成中的应用. 磷叶立德(P-ylide) [6] 是一类具有内鎓盐结构的碳负离子亲核试剂, 在有机合成中具有重要的用途. 例如, 磷叶立德参与的 Wittig 反应 [7] 已成为有机合成中构建碳碳双键最有效的方法之一. 烯丙基磷叶立德(Allylic P-ylide) [8] 是一类特殊结构的磷叶立德, 其中磷叶立德的碳负离子直接与烯基相连, 可发生碳负离子的离域, 从而表现出比简单磷叶立德更丰富的反应性(Scheme 1). 根据 vinylogy 规则, 烯丙基磷叶立德的 α 位碳的性质能够传递至 γ 位碳, 通过 γ 碳参与亲核进攻, 可实现 vinylogous 类型有机反应(Scheme 1). Schneider 等 [9] 通过氢溴酸淬灭实验表明, 烯丙基磷叶立德在低温(-78

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Phosphine-Mediated Olefination between Aldehydes and Allenes: An Efficient Synthesis of Trisubstituted 1,3-Dienes with High E-Selectivity

Cited by 58 publications

References 53 publications

Phosphine Organocatalysis

Phosphine Organocatalysis

Recent advances in stoichiometric phosphine-mediated organic synthetic reactions

Progress on Vinylogous Organic Reactions of Allylic Phosphorus Ylides with Carbonyl Compounds

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