CAS: New Advances in Sustainable Catalysis

在化学系化学催化项目的支持下，圣巴巴拉的加州大学的布鲁斯·利普舒茨教授正在研究几种方法，以专门使用水作为反应溶剂，而不是常见的产生废物的有机溶剂。使这种转换为水的关键技术，自然用于化学反应，是基于在水溶液中形成纳米颗粒（NP）。纳米颗粒被设计成浓缩试剂和催化剂，从而使通常在单独的水中无法发生的反应能够发生。此外，考虑到每个NP内反应物和催化剂的高浓度，将不再需要所需的高温，从而降低了适用于该系统的工艺的能量成本。这些新的进展预计将有助于有机化学的转变，一般来说，必须避免其对石油的依赖，从石油衍生出许多通常使用的有机溶剂。为了进一步帮助这种过渡到一个更水基学科，将创建一个手册，其中包含实验，所有在室温下在水中进行，供世界各地的大二有机实验室使用。目的是在很早的阶段就向学生介绍水中化学。根据化学系化学催化计划的这一奖项，圣巴巴拉的加州大学的布鲁斯·利普舒茨教授和他的团队将从事三个主要研究方向：（1）化学酶催化的创新，其中相容性问题已经阻止了涉及在单个反应容器中在水中使用的化学催化和酶促方法的该领域的发展，通过在缓冲的水性介质中加入少量表面活性剂来简化和促进;（2）原位形成选定的硫代酯，然后使其与原位生成的有机锌试剂反应，从而导致在一锅中和在水中制备不对称酮的新途径;以及（3）基于纳米胶束阵列中存在的非典型情况发展了有机化学中的新概念;即高浓度和有限的反应物和催化剂流动性作为提高对映选择性（EE）的手段，而不是传统的在低温下使用有机溶剂。如果这一发现被证明是普遍的，即ee可以通过利用水胶束介质来最大化，潜在地减少对昂贵的低温反应条件的依赖以实现和保持低温，这将是对催化的重要补充，也是推进水中化学的重要一步。PI和他的团队致力于精细化工行业，特别是制药行业，以便将这些进步应用于实际应用。该奖项反映了NSF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。

With the support of the Chemical Catalysis program in the Division of Chemistry, Professor Bruce Lipshutz of the University of California at Santa Barbara is studying several approaches to the exclusive use of water as a reaction solvent, rather than the common, waste-generating organic solvents. The key technology enabling this switch to water, which Nature uses for chemical reactions, is based on the formation of nanoparticles (NPs) in the aqueous solutions. The NPs are designed to concentrate reagents and catalysts, thus enabling reactions to occur that would normally fail in water alone. Moreover, given the high concentrations of reactants and catalyst within each NP, high temperatures needed will no longer be required, reducing energetic cost of processes amenable to this system. These new advances are expected to contribute to the shift that organic chemistry, in general, must make to avoid its dependence on petroleum, from which derive many of the organic solvents typically used. To further assist with this transition to a more aqueous-based discipline, a Manual will be created containing experiments, all to be done in water at room temperature, for use in sophomore organic laboratories worldwide. The intention will be to introduce students at a very early stage to chemistry in water. Under this award from the Chemical Catalysis program in the Division of Chemistry, Professor Bruce Lipshutz of the University of California at Santa Barbara and his team will pursue three main research directions: (1) innovations in chemoenzymatic catalysis, where the compatibility problem that has prevented the advancement of this field involving both chemocatalytic and enzymatic processes to be used in water in a single reaction vessel has been streamlined and facilitated by adding small amounts of a surfactant in the buffered aqueous medium; (2) the in situ-formation of selected thio-esters that are then subject to reaction with in situ-generated organozinc reagents, thereby leading to a new route to unsymmetrical ketones, in one pot and in water; and (3) development of a new concept in organic chemistry based on the atypical situation that exists within nano-micellar arrays; that is, high concentrations and limited reactant and catalyst mobility as a means of enhancing enantioselectivities (ee’s), rather than the traditional use of organic solvents at low temperature. Should this discovery prove to be general; that ee’s can be maximized by utilization of aqueous micellar media, potentially reducing dependence upon costly cryogenic reaction conditions to achieve and maintain low temperatures, this will be both an important addition to catalysis and a major step forward in advancing chemistry in water. The PI and his group are engaged with the fine chemical industry, in particular the pharmaceutical industry, so as to bring these advances to practical application.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.