Development of Highly Slective Reactions Using Allylic Barium Reagents

使用烯丙基钡试剂开发高选择性反应

• 批准号: 07555286
• 负责人: YAMAMOTO Hisashi
• 金额: $ 5.5万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07555286/
• 关键词: Allylic Barium Reagent; Selective Allylation; alpha-selectivity; Allylic Halide; Epoxide; Imine; Phosphate; Barbier-Type Cross-Coupling Reaction; α選択的カルボキシル化反応; 選択的アリル化反応; ビス(2,2,2-トリフルオロエチル)リン酸エステル

The organomatallic compounds of heavier alkaline earth metals have found little application in organic synthesis, since they do not offer any advantages over Grignard reagents. We have been interested in using barium or strontium reagents with the anticipation that such species should exhibit markedly different stereochemical stability from that the ordinary magnesium reagent. We have already reported that the allylic barium reagents can be easily prepared from in situ generated reactive barium and allylic chlorides, and react with a variety of carbonyl compounds at-78ﾟC to produce the homoallylic alchols with remarkably high alpha-selectivity and retention of the configuration of the starting chloraide.In this research, we further examined the reactions of allylic barium reagents with other electrophiles and thus highly alpha-selective allylation reactions with allylic halides, epoxides, and imines were found. Noteworthy was the fact that aldimines were transformed into homoallylic amines by treatment with allylic barium reagents in which both the alpha-and gamma-adducts were selectively obtained by simply changing the reaction temperature. Bis(2,2,2-trifluoroethyl)phoshate was found to be a superior leaving group for alpha, alpha'-selective cross-coupling reaction of allylic alcohol derivatives with allylic barium reagents. Selective Barbier-type cross-coupling reation was also achieved using this leaving group. For example, when a 1 : 1 mixture of (E) -2-octenyl 1-bis (2,2,2-trifluoroethyl) phosphate and (E) -2-decenyl chloride was teated with 1 equiv of reactive barium, the cross-coupling products were obtained with 86% selectivity and an alpha, alpha'/alpha, gamma' ratio of 94 : 6 . For practical use, largescale carboxylation of an allylic barium reagent was also investigated and over 70% yield of the product was constantly obtained in the 7 mmol-scale reaction.

重碱土金属的有机金属化合物在有机合成中几乎没有应用，因为它们与格氏试剂相比没有任何优势。我们一直对使用钡或锶试剂感兴趣，期望这些物质应表现出与普通镁试剂明显不同的立体化学稳定性。我们已经报道了烯丙基钡试剂可以很容易地由原位生成的反应性钡和烯丙基氯化物制备，并在-78 ℃下与各种羰基化合物反应，以非常高的α-选择性和保留起始氯代物的构型生成高烯丙基醇。我们进一步研究了烯丙基钡试剂与其它亲电子试剂的反应，并因此研究了与烯丙基卤化物，环氧化物，值得注意的是，醛亚胺转化为高烯丙基胺的处理与烯丙基钡试剂，其中α-和γ-加合物选择性地获得通过简单地改变反应温度。双（2，2，2-三氟乙基）磷酸酯是烯丙醇衍生物与烯丙基钡试剂的α，α '-选择性交叉偶联反应的一个上级离去基团。利用该离去基团还实现了选择性的Barbier型交叉偶联反应。例如，当（E）-2-辛烯基1-双（2，2，2-三氟乙基）磷酸酯和（E）-2-癸烯基氯的1 ∶ 1混合物与1当量的反应性钡反应时，以86%的选择性和94 ∶ 6的α，α ′/α，γ ′比获得交叉偶联产物。为了实际应用，还研究了烯丙基钡试剂的大规模羧化反应，在7 mmol规模的反应中，产物的产率一直保持在70%以上。

项目成果

A.Yanagisawa et al.: "Regio-and Stereoselective Synthesis of 1,5-Dienes Using Allylic Barium Reagents" Bull.Chem.Soc.Jpn.68. 1263-1268 (1995)

A.Yanagisawa 等人：“使用烯丙基钡试剂区域和立体选择性合成 1,5-二烯”Bull.Chem.Soc.Jpn.68。

A.Yanagisawa et al.: "Highly Regioselective Allylation of Imines with Allylic Barium Reagents" J.Chem.Soc.Chem.Commun.367-368 (1996)

A.Yanagisawa 等人：“用烯丙基钡试剂对亚胺进行高度区域选择性烯丙基化”J.Chem.Soc.Chem.Commun.367-368 (1996)

K.Yasue et al.: "Regioselective Coupling Reaction of Allylic Barium Reagents with Epoxxides" Bull.Chem.Soc.Jpn.(in press).

K.Yasue 等人：“烯丙基钡试剂与环氧化物的区域选择性偶联反应”Bull.Chem.Soc.Jpn.（印刷中）。

A. Yanagisawa: "Regio-and Stereoselective Carboxylation of Allylic Barium Reagents : (E)-4, 8-Dimethyl-3, 7-nonadienoic Acid" Org. Synth.(印刷中).

A. Yanagisawa：“烯丙基钡试剂的区域选择性羧化：(E)-4, 8-二甲基-3, 7-壬二烯酸” Org。

A. Yanagisawa: "Advances in Carbanion Chemistry, Volume 2" JAI Press Inc., 24 (1996)

A. Yanagisawa：“碳负离子化学进展，第 2 卷”JAI Press Inc.，24 (1996)