Studies on Stereoregulated Reaction Using Organosilicon Reagents and Highly Selective Synteses of Heterocyclic Compounds

有机硅试剂立体调控反应及杂环化合物高选择性合成研究

• 批准号: 01470091
• 负责人: HOSOMI Akira
• 金额: $ 4.22万
• 依托单位: University of Tsukuba (1990)Nagasaki University (1989)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-01470091/
• 关键词: Organosilicon compound; Highly coordinate silicon; allylsilicoate; Azomethine ylids; Selective synthesis; Cross-coupling; Allylation; Stereochemistry; 1,3ー双種子試薬; 有機ケイ素化学; 有機合成化学; ヘテロ環化学; デンドラレン; 交叉共役トリエン; [3+2]環化付加; アルキリデンアゾメチンイリド; チオカルボニル

Much attention has been recently focused on both syntheses of tetracoordinate allylsilanes and their applications to organic synthesis. Allylsilanes whose silicon-allyl sigma-bond is thermally stable can be highly functionalized allvl are transferred onto carbon electrophiles activated by a Lewis acid with high regio-, stereo- and chemoselectivity. One of the most interesting features in organosilicon chemistry is that stable high coordinate species can be isolated. In an extension of organosilicon compounds in organic synthesis, we have found that pentacoordinate allylsiliconates and related compounds, unknown hitherto, can be readily prepared and used as nucleophiles, some of which are reported.Topics are (1) preparations of pentacoordinate allylsiliconates, substituted by alkoxy groups, which are useful and storable reagents, regio-, chemo- and stereoselective allylations of carbonyl compounds without catalyst, and stereochemical outcomes of asymmetric allylation with optically active allylsiliconates which are interpreted by a six-membered cyclic transition state, in sharp contrast with an anti-S_<E'> mechanism for the allylation using tetracoordiante allylsilane, (2) Chemo- and stereoselective reductions of carbonyl compounds using alkoxy-substituted hydridosiliconates derived from trialkoxysilane and alkali metal alkoxides, and new catalytic asymmetric reductions of prochiral ketone using hydridosiliconates. (3) Cross-coupling reactions of alkenylsiliconates with organic halides and triflates catalyzed by a palladium complex in a stereoselective mode. (4) Syntheses of highly reactive species which were hardly obtainable and not isolable were achieved, Organosilicon reagents that acted as a synthetic equivalent of alkylideneazomethine ylids were prepared and allowed to react with alkenes, carbonyl and thicarbonyl compounds to give the corresponding [3+2] cycloadducts in high yields.

四配位烯丙基硅烷的合成及其在有机合成中的应用是近年来研究的热点。硅-烯丙基σ-键是热稳定的烯丙基硅烷可以被高度官能化的烯丙基转移到由刘易斯酸活化的碳亲电体上，具有高的区域选择性、立体选择性和化学选择性。有机硅化学中最有趣的特征之一是可以分离出稳定的高配位物种。在有机硅化合物在有机合成中的应用方面，我们发现五配位烯丙基硅酸酯及其相关化合物可以很容易地制备并用作亲核试剂，其中一些已被报道，主要内容包括：（1）烷氧基取代的五配位烯丙基硅酸酯的制备，羰基化合物的区域、化学和立体选择性烯丙基化反应，和立体化学结果，这与用四配位烯丙基硅烷进行烯丙基化反应的反S_E '机理形成鲜明对比。（2）由三烷氧基硅烷和碱金属醇盐衍生的烷氧基取代的多羟基硅酸酯对羰基化合物的化学和立体选择性还原，以及使用多羟基硅酸酯的前手性酮的新的催化不对称还原。(3)钯配合物催化烯基硅酸酯与有机卤化物和三氟甲磺酸酯的立体选择性交叉偶联反应。(4)合成了一系列不易获得且不易分离的高活性化合物。合成了一种有机硅试剂作为亚烷基甲亚胺叶立德的合成等价物，并使其与烯烃、羰基和硫羰基化合物反应，高产率地得到相应的[3+2]环加合物。

项目成果

A. Hosomi: "Organic Synthesis Utilizing Organosilicon Compounds" Advances in Pharmaceutical Sciences. 5. 80-95. (1989)

A. Hosomi：“利用有机硅化合物进行有机合成”制药科学进展。

A.Hosomi,Y.Miyashiro,R.Yoshida,Y.Tominaga,T.Yanagi and M.Hojo: "Nー(Silylmethyl)ーSubstituted Ketene N,SーAcetals as a Synthetic Equivalent of Novel 1,3ーDipolar Reagent,Alkylideneazomethine Ylids: Synthesis and[3+2]Cycloadditions" J.Org.Chem.55. 5308-5310 (1

A.Hosomi、Y.Miyashiro、R.Yoshida、Y.Tominaga、T.Yanagi 和 M.Hojo：“N-(甲硅烷基甲基)-取代乙烯酮 N,S-缩醛作为新型 1,3-偶极试剂的合成等效物,亚烷基偶氮甲碱 Ylids: 合成和 [3+2] 环加成” J.Org.Chem.55. 5308-5310 (1

A. Hosomi and T. Yanagi: "Highly Selective Organic Synthesis Using Highly Coordinate Organosilicon Compounds" J. Japan Oil Chem. Soc.39(10). 875-880. (1990)

A. Hosomi 和 T. Yanagi：“使用高度配位有机硅化合物进行高选择性有机合成”J. Japan Oil Chem。

A. Hosomi, T. Masunari, Y. Tominaga, T. Yanagi, and M. Hojo: "2-Trimethylsilylethy-1, 3-butadiene as a Synthetic Equivalent of Parent Cross-Conjugated Hexatriene, 3-Methylene-1, 4-pentadiene" Tetrahedron Lett.31(43). 6201-6204. (1990)

A. Hosomi、T. Masunari、Y. Tominaga、T. Yanagi 和 M. Hojo：“2-三甲基甲硅烷基-1, 3-丁二烯作为母体交叉共轭六三烯 3-亚甲基-1, 4- 的合成等价物

A. Hosomi, S, Kohra, and Y. Tominaga: "New Synthetic Reactions Using Alkoxy-Substituted Highly Coordinate Organosilicon Compounds" J. Synth. Org. Chem., Japan. 47(9). 831-842. (1989)

A. Hosomi、S、Kohra 和 Y. Tominaga：“使用烷氧基取代的高度配位有机硅化合物的新合成反应”J. Synth。