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.

我发现钯催化的烯丙醇与 SnCl_2 的羰基烯丙基化反应在空气中的水介质中顺利进行。烯丙醇在制备π-烯丙基钯络合物时充当烯丙基碳负离子的合成子。换句话说，这意味着亲电子的 pi-烯丙基钯配合物的表观电荷反转。烯丙醇的羰基烯丙基化可以通过选择溶剂实现高化学、区域和非对映选择。在此，我报告了这一新工艺的全部范围、局限性和机理： 1. ^1H、^<13>C 和 ^<119>Sn NMR 研究阐明了烯丙醇羰基烯丙基化中的实际烯丙基化剂干燥介质中为烯丙基三氯锡，其制备方法如下：(1) 将烯丙醇氧化加成到具有 SnCl_2 的 Pd(O) 络合物上，(2) 将 SnCl_2 插入到π-烯丙基钯络合物，然后(3)还原消除π-烯丙基三氯锡酸钯。 2. 这种极性溶剂中的羰基烯丙基化已应用于螯合控制的非对映选择； (1) ω-羟基羰基化合物与烯丙基锡中的 Sn (IV) 的螯合， (2) 分子内乙氧基羰基与 1-取代的 2-乙氧基羰基-2-丙烯基锡中的 Sn (IV) 的螯合，以及 (3) 4-取代的4-羟基-2-丁烯基锡中分子内羟基与Sn(IV)的螯合。 3.使用(1)通过2-羟甲基烯丙基乙烯基醚的Claisen重排制备的4-羟甲基-4-戊烯醛和(2)通过3-羟甲基烯丙基乙烯基醚的oxy-Cope重排制备的7-羟基-5-庚烯醛进行分子内羰基烯丙基化。羟基-4-羟甲基-1, 5-己二烯。 4.非极性溶剂中超声促进的3-取代烯丙醇的羰基烯丙基化导致了极性溶剂中羰基烯丙基化的反向区域控制。