Development of Transition-Metal-Catalyzed Reactions of Preparing Allenes and Their Derivatives

过渡金属催化制备丙二烯及其衍生物反应的进展

基本信息

批准号：
17550093
负责人：
OGASAWARA Masamichi
金额：
$ 2.3万
依托单位：
Hokkaido University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2005
资助国家：
日本
起止时间：
2005 至 2006
项目状态：
已结题

项目摘要

Previously, we reported a palladium-catalyzed reaction of 2-bromo-1,3-dienes, which could be easily derived from a variety of aldehydes, with soft nucleophiles giving functionalized allenes. The reaction was extended to an asymmetric counterpart by using a chiral palladium catalyst and the corresponding axially chiral allenes were obtained with excellent enantioselectivity.It was found analogous bromodiene substrates could be prepared from allylsilanes. It was demonstrated that 1,3-dien-2-y1 triflates, which were easily obtained in high yields from vinylketones, showed analogous reactivity to the bromodienes in the Pd-catalyzed reaction. These provided a route to multi-substituted allenes, which were inaccessible by the route from aldehydes.The Pd-catalyzed allene synthesis reaction was applied to asymmetric total synthesis of the sex pheromone of male dried bean beetle.For the Pd-catalyzed asymmetric synthesis of the axially chiral allenes, biaryl bisphosphines, such as binap, were effective for high enantioselectivity. It was found that introduction of bulky substituents at the 3-and 3'-positions of the biaryl skeleton improved the performance of the biaryl chiral phosphines in the Pd-catalyzed reaction.An intermediate of the Pd-catalyzed reaction, alkylidene-π-allylpalladium species, was isolated and its solution dynamics was studied. Based on the results, a novel reaction of 2-bromo-1,3,5-trienes with soft nucleophiles giving conjugated vinylallenes was developed. The reaction was successfully extended to the asymmetric reaction.It was known that 1,4-hydrosilylation of conjugated enynes afforded allenylsilanes. Newly developed chiral phosphaferrocenes were applied to the asymmetric hydrosilylation of enynes and axially chiral allenylsilanes were obtained with excellent enantioselectivity.Treatment of appropriate zirconacyclopentane species with propargyl electrophiles in the presence of copper(I) salts gave bis-allene products in a stereospecific fashion.

以前，我们报道了2-Bromo-1,3-二烯的钯催化反应，可以很容易地源自多种醛，而软核硫杆菌具有功能化的Allenes。通过使用手性钯催化剂将反应扩展到不对称的对应物，并以极好的对映选择性获得了相应的轴向手性艾伦。它被发现可以从Allylsilanes中制备类似的溴化物底物。证明1,3-Dien-2-Y1三叶酸盐很容易从乙烯基酮中获得高产量，在PD催化反应中显示出对溴化剂的类似反应性。这些提供了多脱酸的艾伦的途径，从醛的途径无法访问，PD催化的艾琳合成反应被应用于雄性干bean甲虫的性别符号的不对称总合成。对高对映选择性有效。发现在Biariall骨架的3'位置引入了笨重的替代物，改善了Biariall手性磷在PD催化反应中的性能。烷基二烯 - 丙二烷基的中间体，烷基丙基甲基丙二烷种的中间体，分离了溶液和溶液动力学。基于结果，开发了2-溴-1,3,5三体与软核磷酸盐的新反应。该反应成功地扩展到了不对称的反应。已知1,4-氢化的enynes提供了甲烯基硅烷。将新开发的手性磷脂氟化剂应用于Enynes的不对称氢化，并具有极好的对映选择性，可在铜（I）在BIS-Ollene Prodencation Percencecececececececececececececececececececececececececececececececececececece中进行propargyl Electophiles的适当的锆环烷物种的处理。

项目成果

期刊论文数量（24）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Vinyl Ketones to Allenes : Preparation of 1,3-Dien-2-y1 Triflates and Their Application in Pd-Catalyzed Reaction with Soft Nucleophiles

乙烯基酮转化为丙二烯：1,3-Dien-2-y1 三氟甲磺酸酯的制备及其在 Pd 催化软亲核试剂反应中的应用

DOI：
发表时间：
2005
期刊：
Org. Lett. 7
影响因子：
0
作者：
Yoshika Sekine;Satomi Toyooka;Simon F.Watts;原田俊郎;Kazuhiko Tsukagoshi et al.;Eiji Shirakawa;Hiroyuki Suga et al.;Masamichi Ogasawara
通讯作者：
Masamichi Ogasawara

Kinetic Resolution of Planar-Chiral Ferrocenes by Mo-Catalyzed Enantioselective Metathesis

钼催化对映选择性复分解平面手性二茂铁的动力学拆分