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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，我们报道了钯催化的2-溴-1，3-二烯，这可以很容易地从各种醛衍生，与软亲核试剂得到功能化的联烯的反应。在手性钯催化下，该反应扩展到不对称反应，得到了相应的轴手性联烯，并具有良好的对映选择性。结果表明，1，3-二烯-2-基三氟甲磺酸酯，这是很容易得到的高收率从乙烯基酮，表现出类似的反应性溴二烯在钯催化的反应。将钯催化的联烯合成反应应用于不对称全合成雄性豆角虫性信息素，在钯催化的轴向手性联烯的不对称合成中，联芳基双膦（如binap）具有较高的对映选择性.发现在联芳基骨架的3-和3 '-位引入大体积取代基可以改善联芳基手性膦在Pd催化反应中的性能，分离得到了Pd催化反应的中间体-烷叉-π-烯丙基钯物种，并对其溶液动力学进行了研究.在此基础上，发展了一种新的2-溴-1，3，5-三烯与软亲核试剂反应生成共轭乙烯基联烯的方法。将该反应成功地推广到不对称反应中，已知共轭烯炔的1，4-硅氢化反应可得到烯丙基硅烷。将新开发的手性磷杂二茂铁用于烯炔的不对称硅氢化反应，得到了具有良好对映选择性的轴向手性联烯基硅烷.在铜（I）盐存在下，用炔丙基亲电试剂处理合适的锆杂环戊烷物种，得到了立体定向的双联烯产物.

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）

Preparation and Characterization of 1, 1'-Diphosphaferrocenes with Linearly Fused Six-Membered Carbocycles

线性稠合六元碳环 1, 1-二磷杂二茂铁的制备与表征

DOI：
发表时间：
2007
期刊：
Journal of Organometallic Chemistry 692
影响因子：
0
作者：
K.Takumi;H.Sakamoto;R.M.Uda;Y.Sakurai;H.Kume;K.Kimura;小笠原正道
通讯作者：
小笠原正道

Synthesis of 2,5 -Bis(binaphthyl)-phospholes and Phosphametallocene Derivatives and Their Application in Pd-Catalyzed Asymmetric Hydrosilylation

2,5-双(联萘)-磷杂环磷酯和磷茂金属衍生物的合成及其在Pd催化不对称硅氢加成反应中的应用

DOI：
发表时间：
2006
期刊：
Organometallics 25
影响因子：
0
作者：
H.Sakamoto;T.Yamamura;K.Takumi;K.Kimura;Masafumi Hirano et al.;小笠原正道
通讯作者：
小笠原正道

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

Applications of 4,4'-(Me3Si)2-BINAP in transition-metal-catalyzed asymmetric carbon-carbon bond-forming reactions.