Novel Stable Chiral Ligation for Asymmetric Organoborane Conversions via 10-Substituted-9-borabicyclo[3.3.2]decanes

通过 10-取代-9-硼双环[3.3.2]癸烷实现不对称有机硼烷转化的新型稳定手性连接

• 批准号: 0213595
• 负责人: John Soderquist
• 金额: $ 27.4万
• 依托单位: University of Puerto Rico
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2002
• 资助国家: 美国
• 起止时间: 2002-07-15 至 2006-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0213595&HistoricalAwards=false
• 关键词: Novel; Stable; Chiral; Ligation; Asymmetric

The objectives of this work involve several aspects of organoboron chemistry. Professor Soderquist and his group will first prepare a number of chiral allyl, crotyl, allenyl, and alkynyl boron reagents which contain the 9-borabicyclo[3.3.2]decane framework. The allyl, crotyl, and allenyl reagents will be utilized in asymmetric addition reactions to prochiral aldehydes and ketones. The chiral alkynyl organoboron reagents will be used in asymmetric conjugate addition reactions to enones. Boron NMR will be used to assess the stereoselectivities of these addition reactions. With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. John A. Soderquist of the Department of Chemistry at the University of Puerto Rico. Dr. Stewart will work on the development of organoboron reagents capable of effecting a number of chemical reactions. This group will explore stereoselective addition reactions using molecules containing ketones and aldehydes as substrates. These addition reactions produce molecules which are chiral (have two nonsuperimposable mirror images) and make only one of the two possible forms (a single enantiomer). Development of this family of reactions is one of the most important problems facing the pharmaceutical industry today. Students trained during the course of this work will gain skills needed by the pharmaceutical and speciality chemicals industries which now produces a number of single enantiomer compounds.

这项工作的目标涉及有机硼化学的几个方面。 Soderquist教授和他的小组将首先制备一些含有9-硼双环[3.3.2]癸烷骨架的手性烯丙基、巴豆基、丙二烯基和炔基硼试剂。 烯丙基、巴豆基和联烯基试剂将用于与前手性醛和酮的不对称加成反应。 手性炔基有机硼试剂将用于烯酮的不对称共轭加成反应。 硼NMR将用于评估这些加成反应的立体选择性。 有了这个奖项，有机和高分子化学计划是支持博士约翰A。波多黎各大学化学系的Soderquist说。 Stewart博士将致力于开发能够影响许多化学反应的有机硼试剂。 这个小组将探索使用含有酮和醛的分子作为底物的立体选择性加成反应。 这些加成反应产生的分子是手性的（有两个不可重叠的镜像），并且只产生两种可能形式之一（单一对映异构体）。 这类反应的发展是当今制药工业面临的最重要的问题之一。 在这项工作的过程中培训的学生将获得制药和特种化学品行业所需的技能，现在生产一些单一的对映体化合物。