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Development of New Asymmetric Catalytic Processes

新型不对称催化工艺的开发

基本信息

批准号：
6898880
负责人：
WILLIAM Dean WULFF
金额：
$ 22.69万
依托单位：
MICHIGAN STATE UNIVERSITY
依托单位国家：
美国
项目类别：
财政年份：
2002
资助国家：
美国
起止时间：
2002-06-05 至 2006-05-31
项目状态：
已结题

来源：
https://reporter.nih.gov/project-details/6898880
关键词：
Diels Alder reaction alkylation antineoplastics aziridines chemical synthesis cyclization diazo compound drug design /synthesis /production imines morphine organometallic compounds palladium ritonavir sphingolipids stereochemistry

项目摘要

This proposal has as its goal the development of asymmetric catalytic versions of several synthetically important reactions. Efficient catalysts for asymmetric Diels-Alder reactions and aziridination of imines with diazo compounds have been developed with the vaulted biaryl ligands VAPOL and VANOL Future efforts will be directed to determining the scope, mechanism and synthetic applicstions of these existing processes. The information that has already been gained in the study of the Diels-Alder reaction has been used to design new ligands that are tailored for octahedral Lewis acids. Derivatives of the VAPOL ligand will also be explored as a platform for organo-palladium chemistry. If successful, these ligands will be screened for allylic substitutions, cycloisomerizations of enynes, [3 + 2] cycloadditions of TMM complexes and oxy(aza) palladation / carbonylation reactions. The scope of the asymmetric aziridination will be explored with respect to the imine and diazo substrates in both inter- and intramolecular modes. A method is proposed for the first general method for the alkylation of aziridine -2-carboxylates. Methods will explored for the development of a general method for the synthesis of both alpha-amino acids and beta-amino acids from the asymmetric catalytic aziridination reaction. Some of the targets for the aziridination reaction include morphine, the diamine portion of ritonavir, sphingolipids and the antitumor agent FR-900482.

该提案的目标是发展几种重要合成反应的不对称催化形式。以VAPOL和VANOL为配体，开发了不对称Diels-Alder反应和亚胺与重氮化合物氮丙啶化反应的高效催化剂。今后的工作将是确定这些现有方法的范围、机理和合成应用。在Diels-Alder反应的研究中已经获得的信息已被用于设计适合于八面体刘易斯酸的新配体。 VAPOL配体的衍生物也将被探索作为有机钯化学的平台。如果成功的话，这些配体将被筛选用于烯丙基取代、烯炔的环异构化、TMM络合物的[3 + 2]环加成和氧（氮杂）钯化/羰基化反应。的不对称aziridination的范围将探讨相对于亚胺和重氮底物在分子间和分子内模式。提出了氮丙啶-2-羧酸酯烷基化的第一种通用方法。将探索方法用于开发从不对称催化氮丙啶化反应合成α-氨基酸和β-氨基酸的通用方法。氮丙啶化反应的一些靶点包括吗啡、利托那韦的二胺部分、鞘脂和抗肿瘤剂FR-900482。

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）

A Novel Bis-Thiourea Organocatalyst for the Asymmetric Aza-Henry Reaction.

DOI：
10.1002/adsc.200800214
发表时间：
2008-08-04
期刊：
ADVANCED SYNTHESIS & CATALYSIS
影响因子：
5.4
作者：
Rampalakos, Constantinos;Wulff, William D.
通讯作者：
Wulff, William D.

Mapping the active site in a chemzyme: diversity in the N-substituent in the catalytic asymmetric aziridination of imines.

DOI：
10.1021/ol802431v
发表时间：
2008-12-04
期刊：
Organic letters
影响因子：
5.2
作者：
Zhang Y;Lu Z;Desai A;Wulff WD
通讯作者：
Wulff WD

Highly enantioselective deracemization of linear and vaulted biaryl ligands.

线性和拱形联芳基配体的高度对映选择性去消旋化。

DOI：
10.1021/ol0275769
发表时间：
2003
期刊：
Organic letters
影响因子：
5.2
作者：
Zhang,Yu;Yeung,Siu-Man;Wu,Hongqiao;Heller,DouglasP;Wu,Chunrui;Wulff,WilliamD
通讯作者：
Wulff,WilliamD

Evidence for a boroxinate based Brønsted acid derivative of VAPOL as the active catalyst in the catalytic asymmetric aziridination reaction.