Phosphine-Mediated Stereoselective Reductive Cyclopropanation of α-Substituted Allenoates with Aromatic Aldehydes

Xu, Silong; Zhou, Lun; Ma, Renqin; Song, Haibin; He, Zhengjie

doi:10.1021/ol902747c

Cited by 58 publications

(17 citation statements)

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“…In 2010, He published an efficient route toward functionalized cyclopropanes starting from activated allenoates (Scheme 779). 851 As in the case of cyclopropanations using a cyano ketone and arylidenemalononitriles, the reaction proceeds through a familiar oxaphospholane intermediate (Scheme 775). From the vinylidenesuccinate, the initially generated vinyl phosphonium anion undergoes γ -addition to the aldehyde, leading to the vinylogous ylide 495 .…”

Section: Miscellaneous Topicsmentioning

confidence: 99%

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: Miscellaneous Topicsmentioning

confidence: 99%

Phosphine Organocatalysis

et al. 2018

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“…最近我们小组 [20] 研究了由叔膦与 α-取代联烯酸酯进一步研究发现, 在亲核性较强的叔膦如 PBu 3 或 PPh 2 Me 参与下, 反应的化学选择性则发生了显著改变, 实现了 α-取代联烯酸酯与醛经原位生成的烯丙基磷叶立德 13 的三组分 Wittig 烯化反应 [21] (Eq. 5).…”

Section: Methodsunclassified

“…然而, γ-甲基联烯酸酯(6d)却表现出特殊的反应性, 在芳基膦催化下与醛发生了新颖的[3＋ 2]环加成反应 [27] . 在 5～10 mol% P(4-FC 6 H 4 ) 3 催化下, 于二甲苯中回流反应, 6d 与一系列芳香醛稳定地发生 [20] . 此外, γ-乙基联烯酸酯也能发生相似的[3＋2]环加成反应, 但收率较低.…”

Section: 叔膦催化 γ-甲基联烯酸酯经烯丙基磷叶立德与醛的环化反应unclassified

Studies on Reactivity ofin situGenerated Allylic Phosphorus Ylides with Aldehydes

Xu¹,

He²

2012

Chin. J. Org. Chem.

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This account primarily summarizes our recent work on the reactivity of in situ generated allylic phosphorus ylides with aldehydes. Under the mediation of stoichiometric tertiary phosphines, allylic carbonates or allenoates readily undergo highly stereoselective three-component Wittig and vinylogous Wittig olefination reactions through in situ generated allylic phosphorus ylides. These reactions constitute simple and efficient synthetic methods for polysubstituted 1,3-dienes. Under the catalysis of tertiary phosphines, γ-methyl allenoates chemoselectively undertake several annulations with aldehydes via a key intermediate of allylic phosphorus ylide, providing atom economical synthesis of 5-and 6-membered oxygen heterocycles. By experimental approaches such as deuterium-labeling and NMR monitoring, mechanisms of the above mentioned reactions have also been investigated.

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“…Bis-substituted allenoate were prepared according to the literature procedure 1,2 and stored at 4 ℃ prior to use. All aldimines were prepared following reported procedures 3 .…”

Section: General Informationmentioning

confidence: 99%