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.

较重的合金土金属的有机化合物发现有机合成几乎没有应用，因为它们没有比Grignard试剂具有任何优势。我们一直有兴趣使用钡或锶试剂，并预期这种物种应暴露于与普通镁试剂的立体化学稳定性明显不同。我们已经报道说，可以从原位产生的反应性钡和紫氯化物中轻松制备烯丙基钡试剂，并与各种羰基化合物AT-78 c反应，以产生同型碱，并具有相当高的α-选择性和在其他研究中的抗反应性的α-选择性和保留性。发现高度α选择性的倾向反应与赤液卤化物，环氧化物和亚胺。选择性的Barbier型交叉偶联再动座也被发现是Alpha的优越的离开组，酒精衍生物与Allic Barium Reagents的Alpha's-Selesive交叉偶联反应。使用此离开组，还实现了选择性的Barbier型交叉耦合重新座。例如，当（E）-2-辛基1-二丁基（2,2,2-三氟乙基）磷酸和（E）-2-氯化物的1：1混合物用1等于反应性钡的剂量，以86％的选择性和Alpha，Alpha，Alpha'/Alpha'Alpha，GAM，GAM，GAMAN，GAMAN，GAMAN：6-2-二苯基氯化物。还研究了一项烯丙基钡试剂的大规模羧化，并在7 mmol尺度反应中不断获得超过70％的产物产率。

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: "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)

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。