烯丙基磷叶立德与羰基化合物的Vinylogous类型有机反应研究进展

烯丙基磷叶立德(allylic phosphorus ylides)是一类具有丰富反应性的有机中间体.由于碳负离子离域,烯丙基磷叶立德可通过γ位碳负离子参与亲核进攻,从而实现vinylogous(插烯)类型有机合成反应.综述了烯丙基磷叶立德与羰基化合物的vinylogous类型反应,具体包括vinylogous Wittig烯化反应以及多种环化反应.这些反应拓展了烯丙基磷叶立德在有机合成中的应用,并提供构筑多种重要有机功能分子的新方法.     

原位生成的烯丙基磷叶立德与醛的化学反应性研究

介绍了我们小组最近有关原位生成的烯丙基磷叶立德与醛的化学反应性研究结果.在化学计量叔膦作用下,烯丙基碳酸酯或联烯酸酯经原位生成的烯丙基磷叶立德活性中间体,与醛发生高度立体选择性的三组分Wittig烯化反应和vinylogous Wittig烯化反应,该类反应为合成多取代1,3-二烯衍生物提供了简单、高效的新方法;在催化量叔膦作用下,γ-甲基联烯酸酯经烯丙基磷叶立德关键中间体与醛发生多个膦催化的环化反应,为五元、六元含氧杂环化合物的合成提供了原子经济性的方法.通过氘代实验和核磁跟踪等方法,对上述反应机理进行了初步探索.     

磷叶立德CH2PH3和类磷叶立德自由基∙CHPH3优势构型和C—P键结构的研究

采用MP4/6-311++G(d,p)和B3LYP/6-311++G(d,p)对磷叶立德CH₂PH₃和类磷叶立德自由基∙CHPH₃进行构型优化，从电子密度拓扑分析的角度对C—P键的键结构进行了探讨。得到如下结论：类磷叶立德自由基和磷叶立德的C—P键性质类似，但磷叶立德中π键由两个电子形成，类磷叶立德自由基中π键由一个电子形成，所以前者的π性明显，而后者的π性不明显。类磷叶立德自由基中的这个单电子在碳原子附近，垂直于对称面的方向上运动，有p_(C→P)配键的特征，所以类磷叶立德自由基∙CHPH₃中的C—P键比相应的产物∙CH₂PH₂中的C—P键要弱一些。     

膦亚胺叶立德在杂环合成中的应用

总结了我们课题组应用膦亚胺叶立德的氮杂Wittig反应合成氮杂环的研究工作.我们发展了一种应用α-酯基膦亚胺与异氰酸酯(或二硫化碳)、亲核试剂的连续成环反应,合成咪唑啉酮及唑类杂环的新方法.应用β-酯基膦亚胺与异氰酸酯(或二硫化碳)、亲核试剂的连续成环反应,则可制备(稠合的)喹唑啉酮和嘧啶酮类杂环.而应用β-炔基膦亚胺与异氰酸酯、亲核试剂在银离子催化下的连续成环反应,可得到吲哚类杂环.最近我们课题组又初步将膦亚胺叶立德应用于串联的Ugi和Passerini后修饰反应中,合成了多取代苯并嗪和喹唑啉类杂环化合物.     

Wittig/Michael串联反应高效合成含有磷叶立德的吲哚并喹唑啉酮衍生物

以吲哚并[2,1-b]喹唑啉-6,12-二酮（色胺酮）及三苯基膦乙酸乙酯（酯基磷叶立德）为原料,在二氯甲烷中反应2 h,经Wittig/Michael串联反应,以高达99%的收率一步合成了15个含有吲哚并喹唑啉骨架的磷叶立德衍生物。其代表产物的结构经X-ray单晶衍射进行确证,化合物结构经¹H NMR, ¹³C NMR, ³¹P NMR, ¹⁹F NMR和HR-MS（ESI-TOF）表征。     

由炔的金属烯丙化合成二烯烃和环烯烃

炔的金属烯丙化(allylmetallation)是炔的金属烃化反应(carbometallation)的一种,是立体专一地合成多取代烯烃的有效途径。铝烯丙化(allylalumination)和锌烯丙化(allyl-     

合成偕二卤代烯烃的新方法

以芳醛为原料,与四卤化碳和三苯基膦发生叶立徳反应合成系列偕二卤代烯烃类化合物（2a～2h）,其结构经¹H NMR和¹³C NMR确证。考察了碱、溶剂、反应温度和反应时间对2产率的影响。结果表明：在最优条件(三乙胺为碱,二氯甲烷为溶剂,于室温反应15 h)下,2产率高达88%。     

手性蒎烯酮亚胺用于立体选择性合成

研究了一系列新蒎烯酮亚胺用于不对称烷基化, 羰基加成和双手性诱导反应。具有π结构的烯酮亚胺具有90%~~99%的立体选择性, 它们可用我们提出的过渡模型来解释。     

含氟磷亚胺化合物的合成及其氮杂-Wittig反应的初步研究

以氟烷基叠氮化合物为原料,合成了含氟磷亚胺化合物,并对其氮杂-Wittig反应进行初步研究,通过^1H NMR,^19F NMR,IR,MS及元素分析对化合物的结构进行了表征。     

非对映选择性可调的甘氨酸酯与亚胺的高对映选择性Mannich反应

J.Am.Chem.Soc.2008,130,14362～14363光学活性α,β-二氨基酸是一类重要的合成中间体,也是许多具有各种生理活性化合物的重要结构片段.甘氨酸酯衍生物和亚胺的Mannich反应是合成这类化合物的有效方法之一,至今已有多种手性金属催化剂和有机催化剂应     

Stereoselective synthesis of Z alkenyl halides via Julia olefination

Julia olefination between alpha-halomethyl sulfones and a variety of aldehydes afforded alkenyl halides in good to excellent yields with high E/Z stereoselectivities. Sulfones were readily prepared in two or three steps from commercially available reagents in good yields. Optimization revealed that the nature of the solvent, the base, and the additive were crucial to obtain the desired alkenyl halides.     

Studies on Phosphonium Ylides,XXIV: Reactions of Phosphorus Ylides with 1,2,3,4-Tetrahydro1-Naphthylidene-Malononitrile

1,2,3,4-tetrahydro-1-naphthylidene-malononitrile (1) reacts with carbethoxymethylene and carbmethoxymethylene- triphenylphosphoranes (2a, 2b) to give the new phospho-ranylidenecyclopentaylidene products (4a, 4b, and 5), respectively. The treatment of (1) with phosphorus ylide 2c afforded the new phosphonium ylide 6. Moreover, the application of reagent (2d) on (1) renders compound 7. On the other hand, when N-phenyliminotriphenylphosphorane (3) reacts with (1), the corresponding adduct (8) was obtained together with triphenylphosphine. Mechanisms accounting for the formation of new products are discussed, and probable structures of products are presented based on analytical and spectroscopic data.     

New aromatizational transformations of 4-methyl-4-trichloromethyl-substituted 2,5-cyclohexadiene triphenylphosphonium and pyridinium ylides: Abstraction or 1,6-migration of the CCl3 group

4-methyl-4-trichloromethylcyclohexadiene triphenylphosphonium ylide obtained by treatment of (1-methyl-1-tricholoromethylcyclohexa-2,4-dien-4-yl)-triphenylphosphonium bromide with BuⁿLi in THF is stabilized by the abstraction of the CCl₃ group to give (p-tolyl)triphenylphosphonium cation, which was isolated as the corresponding hydroxide. Conversely, an analogous pyridinium ylide, obtained by treatment ofZ/E stereoizomericN-(1-methyl-1-trichloromethylcyclohexa-2,5-dien-4-yl)pyridiunium bromide with a base (piperidine in CD₂Cl₂, BuⁿLi in THF), at temperatures above −40 °C, undergoes a novel high-yield aromatizational skeletal rearrangement with migration of the CCl₃ group to position 2 of the heterocycle. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 386–388, February, 1997.     

First Example of Highly Stereoselective Synthesis of 1,2,3‐Trisubstituted Cyclopropanes via Chiral Selenonium Ylides

A new strategy for the highly stereoselective synthesis of three stereoisomers of chiral 1,2,3‐trisubstituted cyclopropanes in good yields with excellent diastereoselectivities and very high enantioselectivities (up to >99 % ee) was developed via selenonium ylides (see scheme). Possible pathways for the asymmetric cyclopropanations were also proposed.

     

Chemistry of Phosphorus Ylides. Part 36 Reactions of 2-Hydroxyisoindole-, Isoindoline-, and Indane-1,3-Dione With Stable and Active Phosphonium Ylides

Abstract

The stabilized alkylidenephosphoranes namely, acetyl-, benzoyl-, methoxycarbonyl-, and ethoxycarbonyl-methylenetriphenylphosphorane react with 2-hydroxyisoindole-1,3-(2H)dione to give the corresponding isoindoline-ylidenes, along with triphenylphosphane oxide. On the other hand, the reaction of active phosphacumulenes, (N-phenyliminovinylidene)-, and (2-oxovinylidene)-triphenylphosphorane with hydroxyisoindole-, isoindoline-, and indane-1,3-dione afforded phosphanylidenecyclobutylidenes derivatives, together with triphenylphosphane oxide. Mechanisms accounting for the formation of the new products are discussed. The antimicrobial activities for the new compounds are also reported.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Cu(I)-catalyzed coupling reactions of fluorinated imidoyl halides with terminal alkynes: Convenient synthesis of fluorinated alkynyl imines

The first example of coupling reactions of fluorinated imidoyl halides with terminal alkynes catalyzed by CuI is presented. Each reaction needed no ligand, and fluorinated alkynyl imines were obtained with excellent yields.     

Studies on Phosphonium Ylides-XXIII: The Behavior of Active and Stabilized Phosphonium Ylides Towards Thiohydantoins

Thiohydantoin 1 reacts with 2-oxovinylidenetriphenylphosphorane (2) to give 1-methyl-2-thioxo-6-(triphenyl-λ⁵-phosphoranylidene)-hexahydro-furo[2,3-d]imidazol-5-one (5). On the other hand, when 1 reacts with phosphorus ylides 3a–d, the respective olefinic adducts 6a, 6b, 8, and the dimeric product 7 were obtained together with triphenyl-phosphine oxide. Moreover, the application of reagent 4 on 1 renders the new product 4-methyl-2,3-diphenyl-2,3,4,6-tetrahydro-1-oxa-1,3,4,6-tetra-azapentalene-5-thione. Mechanisms accounting for the formation of the products are presented based on analytical and spectroscopic data.