Organocatalysis with N-heterocyclic carbenes via new reactive intermediates

下面的建议描述了n -杂环碳（NHC）衍生的亚砜基偶氮中间体在有机催化中的潜力。这些的结果将是传递新的和对映选择性，催化反应以及复杂分子结构的新合成策略。2009年发现羧酸氧化态起始物质通过酰基偶氮中间体参与路易斯碱NHC催化。2015年，Lupton小组在一项初步研究中报告了磺酰唑中间体，该中间体具有在NHCs介导的一系列转化中被利用的潜力。在这些结果的基础上，主要目的是开发其类似物亚砜酰唑及其相关中间体的化学性质，并开发亚砜酰唑在对映选择性γ -sultine合成中的应用。研究的重点是发现一锅双催化NHC环化/Pd芳基化，以研究sultine结构的潜在用途。在此基础上，进一步研究亚砜酰唑的环化转化为β -sultin产物，并探索相关的亚砜酰唑碳离子和烯丙基阴离子在反应发现中的化学性质。这里详细的研究构成了这个未知领域的切入点，这个领域很可能显示出显著的多样性，从而实现一系列的反应设计。

The following proposal describes studies focused on the potential of N-heterocyclic carbene (NHC) derived sulfinyl azolium intermediates in organocatalysis. The outcome of these will be the delivery of new and enantioselective, catalytic reactions as well as novel synthetic strategies to complex molecular structures. In 2009 it was discovered, that carboxylic acid oxidation state starting materials engage in Lewis base NHC catalysis via acyl azolium intermediates. The sulfonyl azolium intermediate was reported 2015 in a preliminary study by the Lupton group and has the potential to be exploited in an array of transformations mediated by NHCs. Based on these results, the principle aim is to develop the chemistry of its analogue, the sulfinyl azolium and related intermediates, and exploit the sulfinyl azolium in an enantioselective gamma-sultine synthesis. studies focused on the discovery of a one-pot, dual catalytic NHC annulation/Pd arylation will be undertaken to investigate potential utility of the sultine structures. Furthermore, studies towards annulative transformations of the sulfinyl azolium to beta-sultine products and finally, exploration of the chemistry of related sulfinyl azolium carbanions and allyl anions in reaction discovery will be undertaken. The studies detailed herein constitute an entry point to this yet unknown field which may well display significant diversity allowing a range of reaction designs to be realised.