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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SnCl2在水介质中的羰基烯丙基化反应在空气中进行得很顺利。烯丙醇作为烯丙基碳负离子的合成子，制备了pi-烯丙基钯配合物。换句话说，这意味着亲电的pi-烯丙基钯配合物的电荷明显反转。烯丙醇的羰基烯丙化反应通过溶剂的选择可以实现高的化学选择性、区域选择性和非对映选择性。在这里，我报告了这个新工艺的全部范围、局限性和机理：1.1H，^&lt；13&gt；C和^&lt；119&gt；锡的核磁共振研究表明，在干燥介质中，烯丙醇与三氯代锡的羰基烯丙基化反应中，实际的烯丙化试剂是烯丙基三氯锡，它是通过(1)烯丙醇与SnCl2氧化加成到Pd(O)的络合物中，(2)将SnCl2插入到pi-烯丙基钯的络合物中，然后(3)还原消除pi-烯丙基钯三氯锡酸盐而得到的。2.在极性溶剂中的这种羰基烯丙化反应已被应用于络合控制的非对映选择性；(1)欧米茄-羟基酮化合物与烯丙基锡中的锡(IV)的络合反应；(2)分子内乙氧基与1-取代的2-乙氧基酮-2-丙烯基锡中的锡(IV)的络合反应；(3)分子内羟基与4-取代的4-羟基-2-丁烯基锡中的锡(IV)的络合反应。3.用2-羟甲基烯丙基乙烯基醚Claisen重排得到的4-羟甲基-4-戊烯和3-羟基-4-羟甲基-1，5-己二烯的氧位重排得到的7-羟基-5-庚烯，进行了分子内的羰基烯丙基化反应。4.超声波促进的3-取代烯丙醇在非极性溶剂中的羰基烯丙基化反应对极性溶剂中的羰基烯丙基化反应产生了反转区域控制。