Stereoselective Reductive Condensation Reactions

描述（由申请人提供）：在此提案中，描述了一个旨在开发新颖且具有合成价值的立体选择性催化还原缩合反应的计划。在我们的初步研究中，我们开发了催化对映选择性还原性醛醇反应，将市售的硅烷，丙烯酸酯和醛转化为醛醇加合物。与基于助剂和Mukaiyama的醛醇工艺相比，还原性醛醇反应具有优势，因为还原性醛醇反应直接提供硅基保护的醛醇加合物，在室温下进行，并直接在市售材料上进行操作。在拟议的研究中，我们的目标是开发具有类似操作简单性的相关工艺，但提供当前催化不对称工艺不易获得的反应产物。由于这些反应使用了非亲氧的晚期过渡金属催化剂，我们怀疑我们开发的还原缩合过程可能在极低的催化剂负载（小于0.05 mol %）下进行，并且不会受到多氧底物催化剂中毒的并发症的影响。

DESCRIPTION (provided by applicant): In this proposal, a program directed towards the development of novel and synthetically valuable stereoselective catalytic reductive condensations reactions is described. In our initial studies we have developed the catalytic enantioselective reductive aldol reaction which converts commercially available silanes, acrylates and aldehydes to aldol adducts. The reductive aldol reaction holds an advantage over auxiliary-based and Mukaiyama aldol processes in that the reductive aldol reaction directly provides silyl protected aldol adducts, proceeds at room temperature and operates directly on commercially available materials. In the proposed research, we aim to develop related processes that have similar operational simplicity but which afford reaction products which are not readily available by current catalytic asymmetric processes. Since non-oxophilic late transition metal catalysts are used for these reactions, we suspect that the reductive condensation processes we develop may proceed at exceptionally low catalyst loading (less than 0.05 mol percent) and not suffer from complications involving catalyst poisoning by polyoxygenated substrates.