CAREER: Novel diastereoselective bond forming reactions via siliconate intermediates

虽然原位硅醇盐形成，然后氢化物还原氧碳正离子是合成上非常有价值的工具，但合成界非常希望将这种初始观察扩展到包括基于碳的转移。 因此，硅醇盐形成的可能性，基于碳的亲核转移到氧代碳阳离子，提供新的非对映选择性碳-碳键，以及伴随的初始羟基“定向”基团的甲硅烷基化是一个巨大的目标，该奖项涉及环状和非环状立体控制。 该项目将进一步研究碳基亲核试剂的加入，这将大大扩展反应序列，超出氧碳正离子的氢化物还原。 这种类型的碳基团转移应允许形成依赖于氧代碳正离子取代模式的季碳或叔碳，并将对立体控制的碳-碳键形成产生巨大影响。 此外，这个职业奖的教育部分将提供一个“真实的世界”的研究经验，高度积极性，代表性不足的少数民族高中学生从农村亚拉巴马。 该奖项将把这些年轻人带入实验室，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物理科学未来职业的兴趣。 有了这个奖项，有机和高分子化学计划是支持教授迈克尔P.詹宁斯的化学系在亚拉巴马，塔斯卡卢萨大学的研究。 Jennings教授的研究工作围绕着在天然产物合成的更大背景下对oxocarbenium阳离子还原的发展和进一步的基本理解。 该方法的成功开发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.