SILOXANE COUPLINGS AND NATURAL PRODUCT SYNTHESIS

硅氧烷偶联剂和天然产物合成

• 批准号: 6377292
• 负责人: PHILIP Ridley DESHONG
• 金额: $ 29.98万
• 依托单位: UNIV OF MARYLAND, COLLEGE PARK
• 依托单位国家: 美国
• 财政年份: 1999
• 资助国家: 美国
• 起止时间: 1999-07-02 至 2003-06-30
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/6377292
• 关键词: allyl compound; antineoplastic antibiotics; biological products; chemical synthesis; colchicine; esters; silicon compounds

DESCRIPTION: (Applicant's Abstract) The long term goal of this research is to determine the scope and limitations of the palladium-catalyzed cross-coupling of hypervalent siloxanes with allylic ester and aryl derivatives. This methodology could serve as an alternative to Stille and Suzuki coupling protocols that have several limitations in the field of natural product synthesis. In this study, the reactions of aryl, vinyl, and allyl siloxanes with a variety of substrates will be investigated. In addition, evaluation of new palladium catalysts for cross-couplings with aryl chlorides and the use of chiral ligands for an asymmetric version of the cross-coupling reaction will be undertaken. Once the scope of the coupling methodology has been determined, the siloxane methodology will be employed for the total synthesis of the antitumor antibiotic (+)-pancratastatin and the antimitotic agent (-)-colchicine.

描述：(申请人摘要)这项研究的长期目标是 确定钯催化的交叉偶联的范围和局限性 含有烯丙基酯和芳基衍生物的高价硅氧烷。这 方法论可以作为Stille和Suzuki耦合的替代方法 在天然产品领域有几个限制的协议 综合。在本研究中，芳基、乙烯基和烯丙基硅氧烷的反应 将对具有各种底物的情况进行调查。此外，还评估了 新型钯催化剂与芳基氯化物的交叉偶联及其应用 交叉偶联反应的不对称版本的手性配体将是 承担了。一旦确定了耦合方法的范围， 抗肿瘤药物的全合成将采用硅氧烷方法学。 抗生素(+)-潘拉他丁和抗有丝分裂药(-)-秋水仙碱。

项目成果

Synthesis and structural characterization of glucopyranosylamide films on gold.

• DOI: 10.1021/la062678j
• 发表时间: 2007-01
• 期刊: Langmuir : the ACS journal of surfaces and colloids
• 作者: Mridula Kadalbajoo;Juhee Park;A. Opdahl;H. Suda;C. Kitchens;J. Garno;J. Batteas;M. Tarlov;P. DeShong

Application of silicon-based cross-coupling technology to triflates.

• DOI: 10.1021/jo034809g
• 发表时间: 2003-09
• 期刊: The Journal of organic chemistry
• 作者: Shaundra Riggleman;P. DeShong

Palladium-catalyzed cross-coupling of aryl triethylammonium bis(catechol) silicates with aryl bromides using microwave irradiation.

使用微波辐射，钯催化芳基三乙基铵双（儿茶酚）硅酸盐与芳基溴的交叉偶联。

• DOI: 10.1021/ol048044q
• 发表时间: 2004
• 期刊: Organic letters
• 影响因子: 5.2
• 作者: Seganish,WMichael;DeShong,Philip
• 通讯作者: DeShong,Philip

Application of directed orthometalation toward the synthesis of aryl siloxanes.

定向邻位金属化在芳基硅氧烷合成中的应用。

• DOI: 10.1021/jo0492057
• 发表时间: 2004
• 期刊: The Journal of organic chemistry.
• 作者: Seganish,WMichael;DeShong,Philip
• 通讯作者: DeShong,Philip

Application of aryl siloxane cross-coupling to the synthesis of allocolchicinoids.

• DOI: 10.1021/ol061413t
• 发表时间: 2006-08
• 期刊: Organic letters
• 影响因子: 5.2
• 作者: Seganish Wm;P. DeShong