New Methods for Green Organic Synthesis

我们的提案重点是开发铋（III）衍生和铁（II）衍生的刘易斯酸，用于 环境友好的化学合成。各种刘易斯酸将被开发为用于选定的对映选择性反应的绿色催化剂。本提案的第一个目标是开发新的手性Bi（III）衍生的催化剂，使得能够进行有效的不对称合成反应，例如向山羟醛和烯丙基化反应。将研究铋盐与选定的手性配体联合用于醛的烯丙基化和巴豆基化反应。最终目标将是开发催化剂，使这些过程能够在水介质中进行。作为我们计划的第二部分，涉及Bi衍生催化，我们计划开发杂环配合物。选择环氧化物开环、亨利和斯特雷克反应来评价双功能催化剂的活性。我们还希望探索新的领域与我们的Fe（II）衍生的不对称催化剂先前描述的不对称Mukaiyama羟醛缩合反应在水介质中。二烯醇甲硅烷基烯醇化物与羰基化合物的反应将进一步研究使用铁（II）盐和C2-对称配体。甲硅烷基二烯醇醚将使用此类手性催化剂进行测试。一些自然的目标将被选中，以突出我们的方法的通用性和多功能性。最后，Fe（II）衍生的手性配合物将作为氧化催化剂进行研究。铁催化的不对称环氧化反应的发展将带来许多优点，因为铁是地球上最丰富的过渡金属，并且相对无毒。首先，我们的建议将包括使用这样的铁配合物作为活性催化剂的烯烃环氧化和二羟基化使用过氧化氢作为终端氧化剂。其次，研究了手性铁配合物在烯酮环氧化反应中的应用。我们建议的目标是开发新的合成方法，重点是催化和对映选择性程序的简单制备生物和商业上重要的分子。我们的研究将有助于开发新的手性刘易斯酸催化剂的创新性绿色合成方法。

Our proposal focuses on the development of bismuth(III)-derived and iron(II)-derived Lewis acids for environmentally benign chemical synthesis. Various Lewis acids will be developed as green catalysts for selected enantioselective reactions. The first objective of this proposal is to develop new chiral Bi(III)-derived catalysts enabling efficient asymmetric synthesis for reactions, such as the Mukaiyama aldol and the allylation reactions. Bi salts conjointly used with selected chiral ligands will be studied for the allylation and the crotylation of aldehydes. The ultimate goal will be to develop catalysts that will enable these processes to be performed in aqueous media. As a second part of our program involving Bi-derived catalysis, we plan the development of heterobimetallic complexes. The epoxide opening, the Henry and the Strecker reactions will be selected to evaluate the activity of the bifunctional catalysts. We also wish to explore new fields with our Fe(II)-derived asymmetric catalysts previously described for the asymmetric Mukaiyama aldol reaction in aqueous media. The reaction of dienol silyl enolates with carbonyl compounds will be further studied using Fe(II) salts and C2-symmetry ligands. Silyl dienol ethers will be tested with such chiral catalysts. A few natural targets will be selected to highlight the generality and versatility of our method. Finally, the Fe(II)-derived chiral complexes will be studied as oxidation catalysts. The development of Fe-catalyzed asymmetric epoxidation should lead to many advantages, as Fe is the most abundant transition metal on the earth and is relatively nontoxic. First, our proposal will include the use of such Fe complexes as active catalysts for alkene epoxidation and dihydroxylation using hydrogen peroxide as the terminal oxidant. Secondly, the chiral Fe complexes will be studied in the epoxidation of enones. The objective of our proposal is the development of new synthetic methods, with emphasis on catalytic and enantioselective procedures for the simple preparation of biologically and commercially important molecules. Our studies will contribute to the development of innovative green synthetic methods using new chiral Lewis acid catalysts.