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Novel Multiple-Component X-C/C-C Formation Reactions

新型多组分 X-C/C-C 形成反应

基本信息

批准号：
6596483
负责人：
Guigen Li
金额：
$ 14.39万
依托单位：
TEXAS TECH UNIVERSITY
依托单位国家：
美国
项目类别：
财政年份：
2003
资助国家：
美国
起止时间：
2003-06-06 至 2007-05-31
项目状态：
已结题

来源：
https://reporter.nih.gov/project-details/6596483
关键词：
Diels Alder reaction alkyl group amides antineoplastics carbonyl compound chemical addition chemical synthesis covalent bond diene esters imides ketones phosphorus compounds stereochemistry

项目摘要

DESCRIPTION (provided by applicant): This NIH R15 proposal is intended to develop novel X-C/C-C bond formation reactions and Diels-Alder cyclization using 1-iodo-3-siloxy-l,3-butadiene (Danishefsky-type diene). The asymmetric catalytic versions of these reaction will be investigated. These reactions can provide efficient approaches to numerous chemically and biologically important compound. For example, a novel lead structure made by the Pl's group has been found to be active toward colon cancer, non-small cell lung cancer and Melanoma as tested by NCI. In the past few years, the PI's group have obtained a substantial amount of preliminary results for the multiple-component X-C/C-C bond formation reaction. The asymmetric halo aldol reaction is the first asymmetric catalytic carbonyl addition of allenolates to aldehydes. Based on our preliminary results, the new asymmetric halo aldol reactions will be carried out by 1,4-robust activation and 1,2-tandem functionalization of alpha,beta-alkylenic ketones. New chiral phosphoramides and polymer beads-attached chiral phosphoramides are designed and will be synthesized as the Lewis base catalysts. Meanwhile, a series of chiral Lewis acid catalysts will be obtained and utilized to control the chirality for the halo aldol and Diels-Alder reactions. The 1,2-difuctionalization of alpha,beta-acetylenic ketones and esters will result in beta-halo Baylis-Hillman adducts which are multiple functionalized. The new catalysts and catalytic systems will result in high regioselectivity, stereoselectivity, chemoselectivity, as well as the scope of substrates for the new reactions. Besides the asymmetric catalysis, chiral p-toluene and tert-butanesulfinimines will also be utilized as the chiral auxiliaries and electrophiles for the novel X-C/C-C bond formation reactions. So far, the PI has trained 21 undergraduates, and fourteen of them achieved publications as co-authors. Most of these students have successfully entered medical or graduate schools in the US. In addition, 6 graduate students have been or are still being trained by PI's synthesis projects. This R15 grant application is very important for the PI to continue his teaching and research activities at Texas Tech.

描述（由申请人提供）：该NIH R15提案旨在开发新的X-C/C-C键形成反应和使用1-碘-3-乙酰基-1，3-丁二烯（Danishefsky型二烯）的Diels-Alder环化反应。将研究这些反应的不对称催化形式。这些反应可以为许多化学和生物学上重要的化合物提供有效的途径。例如，由Pl的小组制造的新型引线结构已经被发现对结肠癌、非小细胞肺癌和黑色素瘤有活性，如NCI所测试的。在过去的几年里，PI的小组已经获得了大量的多组分X-C/C-C键形成反应的初步结果。不对称卤代羟醛缩合反应是第一个联烯醇酯与醛的不对称催化羰基加成反应。基于我们的初步结果，新的不对称卤代羟醛缩合反应将通过α，β-烯基酮的1，4-鲁棒活化和1，2-串联官能化来进行。设计并合成了新型的手性磷酰胺和聚合物珠连接的手性磷酰胺作为刘易斯碱催化剂。同时，我们还将得到一系列手性刘易斯酸催化剂，并将其用于卤代羟醛和Diels-Alder反应的手性控制。α，β-炔属酮和酯的1，2-二官能化将产生多重官能化的β-卤代Baylis-Hillman加合物。新的催化剂和催化体系将导致高的区域选择性，立体选择性，化学选择性，以及为新的反应底物的范围。除了不对称催化外，手性对甲苯和叔丁基亚磺酰亚胺也将作为手性助剂和亲电试剂用于新型X-C/C-C键形成反应。到目前为止，PI已经培养了21名本科生，其中14人以合著者的身份发表了论文。这些学生中的大多数已经成功进入美国的医学或研究生院。此外，6名研究生已经或正在接受PI综合项目的培训。这个R15补助金申请是非常重要的PI继续他的教学和研究活动在德州理工大学。

项目成果

期刊论文数量（11）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Chiral N-phosphonyl imine chemistry: asymmetric additions of ester enolates for the synthesis of beta-amino acids.

手性 N-膦酰亚胺化学：酯烯醇化物的不对称加成用于合成 β-氨基酸。

DOI：
10.1111/j.1747-0285.2008.00682.x
发表时间：
2008-08
期刊：
CHEMICAL BIOLOGY & DRUG DESIGN
影响因子：
3
作者：
Han, Jianlin;Ai, Teng;Nguyen, Thao;Li, Guigen
通讯作者：
Li, Guigen

Manganese (IV) oxide-catalyzed electrophilic diamination of electron-deficient alkenes provides an easy synthesis of alpha,beta-diamino acid and ketone derivatives for peptidomimetic studies.

氧化锰 (IV) 催化缺电子烯烃的亲电二胺化可以轻松合成 α,β-二氨基酸和酮衍生物，用于拟肽研究。

DOI：
10.1111/j.1399-3011.2005.00294.x
发表时间：
2005
期刊：
The journal of peptide research : official journal of the American Peptide Society.
影响因子：
0
作者：
Timmons,C;McPherson,LM;Chen,D;Wei,H-X;Li,G
通讯作者：
Li,G

Construction of a bacterial autoinducer detection system in mammalian cells.