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.

此前，我们报道了 2-溴-1,3-二烯的钯催化反应，该反应可以很容易地衍生自各种醛，与软亲核试剂产生官能化丙二烯。通过使用手性反应，该反应扩展到不对称对应物。钯催化剂和相应的轴向手性丙二烯具有优异的对映选择性。发现可以由烯丙基硅烷制备类似的溴二烯底物。结果表明，1,3-二烯-2-y1三氟甲磺酸酯很容易从乙烯基酮中以高产率获得，在钯催化反应中表现出与溴二烯类似的反应性，这提供了一条制备多取代丙二烯的途径。 Pd催化丙二烯合成反应应用于雄性干豆性信息素的不对称全合成对于 Pd 催化的轴向手性丙二烯的不对称合成，联芳基双膦（例如 binap）可有效提高对映选择性，结果发现在联芳基骨架的 3-和 3'-位引入庞大的取代基可以改善。联芳基手性膦在 Pd 催化反应中的性能。Pd 催化反应的中间体，分离出亚烷基-π-烯丙基钯物质并研究了其溶液动力学，基于该结果，开发了一种新的2-溴-1,3,5-三烯与软亲核试剂生成共轭乙烯基丙二烯的反应。已知共轭烯炔的 1,4-氢化硅烷化可得到新开发的手性磷杂二茂铁。应用于烯炔的不对称氢化硅烷化，得到了具有优异对映选择性的轴向手性丙二烯基硅烷。在铜（I）盐存在下，用炔丙基亲电子试剂处理适当的锆环戊烷物质，以立体有择方式得到双丙二烯产物。

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