New Methods for Green Organic Synthesis

我们的建议侧重于开发铁和铋衍生的路易斯酸作为绿色催化剂。它们在合成化学中的应用需要进一步发展，因为与其他金属相比，它们对环境无害，相对无毒且经济。我们的研究目标是开发新的合成方法，重点是催化和对映选择程序，以直接制备药物感兴趣的分子。在现代有机合成中，催化不对称过程对于生产对映异构富集化合物是必不可少的，与需要化学计量量的手性试剂的方法相比，它提供了更经济、更环保的过程。我们的研究结果将为制备具有生物学意义的分子提供新的工具。这些研究将有助于开发新的绿色合成方法，使用环境友好和更经济的刘易斯酸催化剂。******我们的建议的第一部分是开发新的手性铁配合物，用于重氮化合物在硅烷的SiH键和CH键上的对映选择性插入反应。首先，利用具有c2对称手性配体的铁盐进行对映选择性插入反应。因此，本文将研究铁类羰基中间体在SiH键上的对映选择性插入反应。手性烯丙基硅烷的对映选择性合成确实具有重要意义。随后用合成的对映体富集的烯丙基硅烷进行羰基化合物的烯丙基化反应。其次，将硅烷用于由铁盐和上述选择的手性配体催化酮类的对映选择性硅氢化反应。各种硅烷将与各种铁盐和手性配体结合使用。制备并评价了新型手性n -杂环碳铁（NHC）催化剂。******我们建议的第二部分将侧重于开发一种高效的烯烃环氧化和二羟基化催化系统。一种能够有效氧化烯烃的生物启发非血红素铁配合物将被开发。初步证据表明，先前制备的FeIIBolm的配体复合物具有适当的几何形状和电子结构，可以作为氧化催化剂。本文还将研究各种铁手性配合物对硫化物的不对称氧化。******我们研究计划的第三部分将致力于双衍生路易斯酸的使用。这些铋配合物将首先用作对映选择性异丁基化反应的催化剂。将制备biii衍生的杂双金属配合物，并将其用作对映选择性反应的催化剂。

Our proposal focuses on the development of iron and bismuth-derived Lewis acids as green catalysts. Their use in synthetic chemistry needs to be further developed because they are environmentally benign, relatively nontoxic and economic in comparison to other metals. The objective of our research is the development of new synthetic methods, with emphasis on catalytic and enantioselective procedures for the straightforward preparation of molecules of pharmaceutical interest. Catalytic asymmetric processes are indispensable for producing enantiomerically enriched compounds in modern organic synthesis, providing more economical and environmentally benign processes than methods requiring stoichiometric amounts of chiral reagents. Our results will lead to new tools for the preparation of molecules of biological interest. These studies will contribute to the development of new green synthetic methods using environmentally friendly and more economical Lewis acid catalysts.******A first part of our proposal deals with the development of new chiral iron complexes for the enantioselective insertion reaction of diazo compounds into the SiH bond of silanes and the CH bond. Firstly, an enantioselective insertion reaction will be developed using Fe salts with C2-symmetric chiral ligands. Consequently, the enantioselective insertion reaction of Fe carbenoid vinyl intermediates into the SiH bond will be studied. The enantioselective synthesis of chiral allyl silanes is indeed of prime importance. The subsequent allylation reaction of carbonyl compounds using the synthesized enantio-enriched allyl silanes will be undertaken. Secondly, silanes will be used in the enantioselective hydrosilylation reaction of ketones catalyzed by iron salts and the above-selected chiral ligands. Various silanes will be employed in combination with a wide selection of Fe salts and chiral ligands. New chiral iron N-heterocyclic carbene (NHC) catalysts will be prepared and evaluated.******A second part of our proposal will focus towards the development of an efficient catalytic system for the epoxidation and dihydroxylation of alkenes. A bioinspired non-heme iron complex capable of efficient oxidation of alkenes will be developed. Initial evidence showed that the previously prepared FeIIBolm's ligand complexes would have the appropriate geometry and electronics to work as oxidation catalysts. The asymmetric oxidation of sulfides using various iron chiral complexes will be studied as well.******A third part of our research program will be devoted to the use of Bi-derived Lewis acids. These Bi complexes will be first used as catalysts for the enantioselective crotylation reaction. BiIII-derived heterobimetallic complexes will be prepared and used as catalysts for selected enantioselective reactions.