Structural Elucidation and Synthetic Application of Organozinc reagents with Pronounced Nucleophilic Reactivity

具有显着亲核反应活性的有机锌试剂的结构解析及合成应用

• 批准号: 04453089
• 负责人: TAMARU Yoshinao
• 金额: $ 4.48万
• 依托单位: Nagasaki University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04453089/
• 关键词: Unsymmetrical Ketone; Palladium Catalysis; Carbon monoxide; Organozinc; Allylic Substrates; Stereoselectivity; Regioselectivity; Umpolung of pi-Allylpalladium; pi-アリルパラジウム; 有機亜鉛代合物; パラジウム; シクロプロパン; 転位反応

(1) The new synthetic reaction of unsymmetrically substituted ketones was developed. The reaction proceeds via the three-component connection reaction of allylic benzoates, carbon monoxide, and organozincs by the catalysis of palladium at room temperature under 1 atm of carbon monoxide. The reaction shows quite characteristic regio (alpha-and gamma-) -and stereoselectivity (inversion of configuration) with respect to the allylic moiety. The reaction is applicable to the combination of a wide structural variety of allylic substrates (benzoates, phosphates) and organozincs (IZn (CH_2)_n X,X=CO_2 Et, CN ; octylzinc iodide, diethylzinc).(2) The new method of umpolung of pi-allylpalladium was developed. The umpolung of pi-allylpalladium takes place cleanly by treatment with diethylzinc via allyl-ethyl transmetallation reaction. The reaction can be catalytic with respect to palladium and the mixture of an allyl benzoate, a carbonyl compound (aldehyde, ketone, ester), diethylzinc, and tetrakis (triphenylphosphine) palladium provides the corresponding homoallyl alcohol in quite high yield. The reaction displays high regio-and stereoselectivity, having been not observed for the allylation with allyzinc halides.

(1)发展了不对称取代酮的合成新反应。该反应通过烯丙基苯甲酸酯、一氧化碳和有机锌的三组分连接反应在室温下在1个大气压的一氧化碳下通过钯的催化进行。该反应显示出相当特征的区域（α-和γ-）-和立体选择性（构型反转）相对于烯丙基部分。该反应适用于多种结构的烯丙基底物（苯甲酸酯、磷酸酯）与有机锌（IZn（CH_2）_nX，X= CO_2Et，CN ;辛基碘化锌，二乙基锌）的结合。(2)研究了烯丙基钯的富集新方法。π-烯丙基钯的还原通过用二乙基锌处理经由烯丙基-乙基transmethalo反应而干净地进行。该反应对于钯是催化性的，苯甲酸烯丙酯、羰基化合物（醛、酮、酯）、二乙基锌和四（三苯基膦）钯的混合物以相当高的产率提供相应的高烯丙醇。该反应显示出很高的区域和立体选择性，没有观察到烯丙基锌卤化物的烯丙基化反应。

项目成果

Y.Tamaru: "Highly Stereoselective Allylation of Aldehdye:Generation of Stereochemicallyl Defined Allylzinc Species via Alky-Allyl Exchange Reaction between π-Allyl…" Angew.Chem. (1995)

Y.Tamaru：“醛染料的高度立体选择性烯丙基化：通过 π-烯丙基之间的烷基-烯丙基交换反应生成立体化学定义的烯丙基锌物种……”Angew.Chem。

K。Yasui: "Palladium(2) Catalyzed Novel Rearrangment of 1-Allyloxy-siloxycyclopropanes。" Tetrahedron Letters. 33. 789-792 (1992)

K.

Y.Tamaru, M.Kimura, S.Tanaka, S.Kure, and Z.Yoshida: ""Convenient Synthesis of 4-Methylene-1,3-oxazolidin-2-ones and 4-Methylene-1,3-oxazin-2-ones via Transition-metal Catalyzed Intramolecular Addition of Nitrogen Atom to Acetylenic Triple Bond"" Bull. Ch

Y.Tamaru、M.Kimura、S.Tanaka、S.Kure 和 Z.Yoshida：“4-亚甲基-1,3-恶唑烷-2-酮和 4-亚甲基-1,3-恶嗪-的便捷合成”

T.Bando, H.Harayama, Y.Fukazawa, M.Shiro, K.Fugami, S.Tanaka, and Y.Tamaru: ""Regio-and Stereoselective Synthesis of 1,3-Hydroxy Amines via Palladium-catalyzed Carbonate-Carbamate Transformation with Unique Stereoselectivity"" J.Org. Chem.59. 1465-1474 (1

T.Bando、H.Harayama、Y.Fukazawa、M.Shiro、K.Fugami、S.Tanaka 和 Y.Tamaru：“通过钯催化的碳酸酯-氨基甲酸酯区域和立体选择性合成 1,3-羟基胺”

Y.Tamaru, H.Sakata, M.Kimura, H.Harayama, H.Konishi, K.Fugami, and S.Tanaka: ""Highly Regio-and Stereoselective Diels-Alder Reaction of Monothiomaleimide, an Ambident C=S and C=C Dienophile"" J.Chem. Soc., Chem. Commun.2365-2366 (1994)

Y.Tamaru、H.Sakata、M.Kimura、H.Harayama、H.Konishi、K.Fugami 和 S.Tanaka：“单硫代马来酰亚胺的高度区域和立体选择性 Diels-Alder 反应，一种环境 C=S 和 C