CAREER: Novel diastereoselective bond forming reactions via siliconate intermediates

虽然原位硅酸盐形成后氧羰基阳离子氢化物还原是一种非常有价值的合成工具，但将这一初步观察扩展到包括碳基转移是合成界非常需要的。因此，硅酸盐形成的可能性，碳基亲核转移到氧羰基阳离子，提供新的非对映选择性碳-碳键，以及伴随的初始羟基“导向”基团的硅基化是本奖项在环和非环立体控制方面的一个巨大目标。该项目将进一步研究碳基亲核试剂的包含，这将大大扩展反应序列，超出氧碳阳离子的氢化物还原。这种类型的碳基团转移应该允许形成依赖于氧羰基取代模式的季碳或叔碳，并将对立体控制碳-碳键的形成产生巨大影响。此外，该职业奖的教育部分将为来自阿拉巴马州农村的高度上进心，代表性不足的少数民族高中生提供“真实世界”的研究经验。这个奖项将把这些年轻人带进实验室，让他们第一次接触科学研究。这种接触将有助于培养和促进对未来物理科学职业的兴趣。有了这个奖项，有机和大分子化学项目支持了塔斯卡卢萨阿拉巴马大学化学系迈克尔·p·詹宁斯教授的研究。詹宁斯教授的研究工作围绕着在天然产物合成的更大背景下对氧羰基离子还原的发展和进一步的基本理解。该方法的成功发展将对制药和农业工业的合成产生影响。

While in situ siliconate formation followed by hydride reduction of an oxocarbenium cation is a synthetically very valuable tool, expansion of this initial observation to include carbon based transfers are highly desirable to the synthetic community. Thus, the possibility of siliconate formation, carbon based nucleophilic shift to an oxocarbenium cation affording new diastereoselective carbon-carbon bonds, and concomitant silylation of the initial hydroxyl 'directing' group is a tremendous goal that this award addresses with respect to cyclic and acyclic stereocontrol. This project will further investigate the inclusion of carbon based nucleophiles which would greatly expand the reaction sequence beyond that of a hydride reduction of the oxocarbenium cation. This type of carbon group transfer should allow for the formation of quaternary or tertiary carbons dependent of the oxocarbenium substitution pattern and will make a tremendous impact on stereocontrolled carbon-carbon bond formation. In addition, the education portion of this CAREER award will provide a 'real world' research experience for highly motivated, underrepresented minority high school students from rural Alabama. This award will bring these young adults into the laboratory for their first encounter with scientific research. This exposure will help to foster and promote interests in future careers within the physical sciences. With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Professor Michael P. Jennings of the Department of Chemistry at The University of Alabama, Tuscaloosa. Professor Jennings' research efforts revolve around the development and further fundamental understanding of oxocarbenium cation reductions within the greater context of natural product synthesis. Successful development of the methodology will have an impact on synthesis in the pharmaceutical and agricultural industries.