LEAPS-MPS: Development of New Photoacid Catalyzed Reactions for Organic Synthesis

该奖项全部或部分由《2021年美国救援计划法案》（公法117-2）资助。在这个由数学和物理科学理事会资助的项目中，Joseph Badillo教授和他在Seton Hall大学的学生将研究光酸和光酸催化，以帮助设计新的化学反应，这些反应将在合成新的有机（碳基）分子中发挥重要作用。光酸在正常状态下是弱酸，只有在光照射下才会变成强酸，从而具有催化活性（能够加速反应）。这种对光活化的依赖提供了传统酸催化无法实现的时间和空间控制。尽管光酸催化具有独特的可能性，但新的光酸的合成和表征以及新的光酸催化反应的发展仍然相对未被探索。Badillo教授还提出了一个扩大参与的计划，包括让他的学生在为URM服务的会议上展示他们的研究，如NOBCChE，与ACS项目SEED合作，为URM的高中生提供研究经验，并与西顿霍尔大学的几个学生组织合作，将科学推广到当地的少数民族高中。Badillo教授将通过测量激发态寿命(t)和酸度（pKa*）进行实验，以提高对常见光酸催化剂的光物理性质的理解。本文将设计、合成和表征一系列不可光消旋的手性光酸，并在C - X （X = H， O， C）成键反应中探索光酸催化的应用，包括不对称激发态质子转移、糖基化和缩醛化反应。在催化的背景下使用光酸发生器，如卤铵和磺胺离子也将进行研究。巴迪罗教授的整合研究和扩大以参与为导向的外展活动的计划，将使被忽视的少数民族高中生到西顿霍尔大学进行研究经验，并将西顿霍尔的学生送到当地学校进行科学外展活动。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

This award is funded in whole or in part under the American Rescue Plan Act of 2021 (Public Law 117-2). In this project, funded by the Mathematical and Physical Sciences Directorate and housed in the Chemistry Division, Professor Joseph Badillo and his students at Seton Hall University will study photoacids and photoacid catalysis to help design new chemical reactions that will be important in synthesizing new organic (carbon-based) molecules. A photoacid is a weak acid in its normal state, and only upon irradiation with light does it become a strong acid, and thus catalytically active (able to speed up reactions). This dependence on light-activation offers temporal- and spatial-control not possible with traditional acid catalysis. Despite the unique possibilities of photoacid catalysis, the synthesis and characterization of new photoacids and the development of new photoacid catalyzed reactions remains relatively unexplored. Prof. Badillo also proposes a broadening participation plan that includes having his students present their research at URM-serving conferences such as NOBCChE, working with ACS Project SEED to provide research experiences for URM high school students, and working with several Seton Hall University student organizations to bring science outreach to local minority-serving high schools.Professor Badillo will perform experiments leading to improved understanding of common photoacid catalysts’ photophysical properties by measuring excited state lifetimes (t) and acidities (pKa*). A series of non-photoracemizable chiral photoacids will be designed, synthesized and characterized, and the use of photoacid catalysis will be explored in the context of C–X (X = H, O, C) bond-forming reactions, including asymmetric excited-state proton transfer, glycosylation, and acetalization reactions. The use of photoacid generators such as halonium and sulfonium ions in the context of catalysis will also be investigated. Prof. Badillo’s plan for integrating research and broadening participation-oriented outreach activities will both bring underrepresented minority high school students to Seton Hall University for research experiences, and send Seton Hall students into local schools for science outreach activities.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.