Development of Organic Synthetic Reaction Utilizing Charge Reversal of pi-Allylpalladium Complex

利用π-烯丙基钯配合物电荷反转的有机合成反应的进展

基本信息

批准号：
02640407
负责人：
MASUYAMA Yoshiro
金额：
$ 1.34万
依托单位：
Sophia University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1990
资助国家：
日本
起止时间：
1990 至 1991
项目状态：
已结题

项目摘要

I have found that palladium-catalyzed carbonyl allylation by allylic alcohols with SnCl_2 smoothly proceeds in aqueous medium under air. Allylic alcohols, preparing pi-allylpalladium complexes, function as synthons of allylic carbanions. In other words, this implies the apparent charge reversal of electrophilic pi-allylpalladium complexes. The carbonyl allylation by allylic alcohols can achieve high chemo-, regio-, and diastereoselection by the choice of solvent. Here I report about the full scope, limitations, and mechanism of this new process : 1. ^1H, ^<13>C, and ^<119>Sn NMR investigation has elucidated that the actual allylating agent in the carbonyl allylation by allyl alcohol in dry medium is allyltrichlorotin, which is prepared via (1) oxidative addition of allyl alcohol to Pd (O) complex with SnCl_2, (2) insertion of SnCl_2 to pi-allylpalladium complex, followed by (3) reductive elimination of pi-allylpalladium trichlorostannate. 2. This carbonyl allylation in polar solvent has been applied to chelation-controlled diastereoselection ; (1) the chelation of omega-hydroxy carbonyl compound to Sn (IV) in allylic tin, (2) the chelation of intramolecular ethoxycarbonyl group to Sn (IV) in 1-substituted 2-ethoxycarbonyl-2-propenyltin, and (3) the chelation of intramolecular hydroxy group to Sn (IV) in 4-substituted 4-hydroxy-2-butenyltin. 3. Intramolecular carbonyl allylation has been carried out using (1) 4-hydroxymethyl-4-pentenals prepared by Claisen rearrangement of 2-hydroxymethylallyl vinyl ethers and (2) 7-hydroxy-5-heptenals prepared by oxy-Cope rearrangement of 3-hydroxy-4-hydroxymethyl-1, 5-hexadienes. 4. Ultrasound-promoted carbonyl allylation by 3-substituted allylic alcohol in nonpolar solvent has caused inversed regiocontrol to the carbonyl allylation in polar solvent.

我发现，钯催化的碳纤维烯烯丙基烯丙基烯丙基酸性醇具有SNCL_2的烯丙基烯丙基烯丙基，在空气下的水性培养基中顺利进行。烯丙基醇，制备pi-Alylpalladium络合物，充当烯丙基碳纤维的合成子。换句话说，这意味着亲电丙酰丙酰胺复合物的明显电荷逆转。烯丙基醇的羰基烯丙基化可以通过选择溶剂来实现高化学，区域和非映选择。 Here I report about the full scope, limitations, and mechanism of this new process : 1. ^1H, ^<13>C, and ^<119>Sn NMR investigation has elucidated that the actual allylating agent in the carbonyl allylation by allyl alcohol in dry medium is allyltrichlorotin, which is prepared via (1) oxidative addition of allyl alcohol to Pd (O) complex with SnCl_2, (2)将Sncl_2插入到pi-Alylpalladium复合物中，然后（3）减少trichlaradium trichlorostannate的消除。 2。极性溶剂中的羰基烯丙基化已应用于螯合控制的非映射。（1）在烯丙基锡中，omega-羟基羰基化合物与Sn（IV）的螯合，（2）在1-构造的2-取代的2-乙氧基 - 氧基 - 2-甲基-2-丙烷基因和（3）中的分子内乙氧基乙氧基核酸组螯合对Sn（IV）的螯合物（IV）。 4-取代的4-羟基-2-丁二烯。 3。已使用（1）4-羟基甲基-4-五邻苯甲酸进行了分子内羰基盟lylation，由Claisen重排制备的2-羟基甲基乙烯基乙烯基乙烯基乙烯基和（2）7-羟基-5-Heptenals由3-Hydroxy-4-Hydroxy-4-Hydroxy-Hydroxy-4-Hydroxy-4-Hydydroxy-4-Hydydroxy-4-Hydroxy-4-Hydydroxy-4-Hydydroxy-4-Hydroxy-4-Hydydroxy-4-Hydroxy rydroxy-4-Hydroxy-4-Hydydroxy组成（2））。 5-杂志。 4。非极性溶剂中的3个取代的烯丙基醇超声促进的羰基烯丙基化已导致极性溶剂中的羰基烯丙基化导致反相反的重新控制。