Convergent Synthesis via Asymmetric Catalysis

通过不对称催化的收敛合成

• 批准号: 8069356
• 负责人: Timothy F Jamison
• 金额: $ 37.99万
• 依托单位: MASSACHUSETTS INSTITUTE OF TECHNOLOGY
• 依托单位国家: 美国
• 财政年份: 2003
• 资助国家: 美国
• 起止时间: 2003-03-01 至 2013-02-28
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/8069356
• 关键词: Acrylates; Aldehydes; Alkenes; Alkynes; Amidines; Area; Biological Factors; Carbodiimides; Carbon; Carbon Dioxide; Catalysis; Chemicals; Coupling; Cyclization; Development; Epoxy Compounds; Esters; Family; Ketones; Literature; Methods; Metric; Nickel; Polymers; Process; Reaction; Squalene; Variant; Work; acrylic acid; base; greenhouse gases; interest; novel; operation; pi bond; polyacrylate; propadiene; research study; sieboldine A

DESCRIPTION (provided by applicant): The focus of this project is the development and application of nickel-catalyzed carbon-carbon bond-forming reactions for the synthesis of medicinally important organic molecules. Methods that we have developed will be utilized in the synthesis of several amphidinolide natural products, sieboldine A, and dioxepandehydrothyrsiferol. None of these has previously been prepared by total synthesis. Two new classes of nickel-catalyzed reactions will be developed. Both involve the coupling of unactivated alpha olefins, which are prepared in metric ton amounts annually. One new class of coupling reaction under development involves electrophiles with cumulated double bonds such as carbon dioxide, ketenes, and carbodiimides. Each of these unites readily available starting materials to make synthetically valuable compounds, acrylic acids, enones, and amidines, respectively. The reactions in the other class all involve conjugate addition reactions, with the advance in this case being that the alpha olefin, an alkene without any obvious activating group, functions as the nucleophile. The focus of this project is the development and application of nickel-catalyzed carbon- carbon bond-forming reactions for the synthesis of medicinally important organic molecules, including amphidinolides, sieboldine A, and dioxepandehydrothyrsiferol. In another part of this project, two new classes of nickel-catalyzed reactions will be developed, and each of these unites readily available starting materials to make synthetically valuable compounds.

描述（由申请人提供）：该项目的重点是镍催化的碳碳键形成反应的开发和应用，用于综合具有药物重要的有机分子。我们开发的方法将用于合成几种两栖类天然产物Sieboldine A和Dioxepandehydrothyrsiferol。这些以前尚未通过总合成来制备。将开发两种新的镍催化反应。两者都涉及未活化的α烯烃的耦合，这些烯烃每年以度量量制备。发育中的一类新的耦合反应涉及具有累积双键的电力，例如二氧化碳，酮和碳二酰亚胺。这些都可以易于使用，以制造合成有价值的化合物，丙烯酸，烯烃和胺。另一类的反应都涉及共轭添加反应，在这种情况下的进展是，α烯烃是无明显激活基团的烯烃，作为亲核试剂。 该项目的重点是镍催化的碳 - 碳键形成反应的开发和应用，用于合成具有药物重要的有机分子的合成，包括两栖类药物，sieboldine A和Dioxepandehydrehydrothyrsiferol。在该项目的另一部分中，将开发两种新的镍催化反应，并且这些既容易获得合成有价值的化合物。