Zinc Atom Transfer-Based Silylzincation of Alkynes

基于锌原子转移的炔烃的甲硅烷基锌化

• 批准号: 208581294
• 负责人: Professor Dr. Martin Oestreich
• 金额: --
• 依托单位: Institut Parisien de Chimie Moléculaire (IPCM)
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2012
• 资助国家: 德国
• 起止时间: 2011-12-31 至 2015-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/208581294?language=en
• 关键词: Zinc; Atom; Transfer; Based; Silylzincation

As part of the current interest in "step-economical" processes to progress towards sustainable chemical synthesis, we wish to develop a new radical-based entry to the silylzincation of alkynes. Inexpensive, non-toxic and with high functional group tolerance, organozincs have regained considerable interest from the chemical community as reagents of choice to develop more selective reactions. A specific feature of alkylzincs is that they can react either as polar nucleophiles (carbanions) or transfer homolytically a zinc group (zinc atom radical transfer) to an alkyl radical. The possibility to combine both types of reactivity in a single reaction has made possible recent multi-component radicalbased approaches to the carbozincation of alkenes and alkynes. Following the same strategy, we envision an approach to the silylzincation of alkynes based on a process wherein a silyl radical would add to a carbon-carbon triple bond to produce a vinylic radical that would be reductively zincated by undergoing a zinc atom radical transfer. The dimetallic 1,2-silylzinc species thus produced are expected to be well suited for in-situ functionalization. In a first research axis we will consider the use of silylzinc reagents. The preparation of new silylzinc reagents having silyl substituted silicon units and the study of their aptitude to transfer homolytically a zinc group will be studied prior to considering inter- and intramolecular additions to alkynes. In a second axis, silylzincation reactions using a combination of a silyl radical precursor and a dialkylzinc reagent will be explored, focusing mainly on intramolecular transformations. Finally, in a third part of the project, the use of 1-silyl-2-zincio alkenes as partners in sequential carbon-carbon bond forming metal-catalyzed crosscoupling reactions will be explored.

作为目前对“步进经济”过程朝着可持续化学综合迈进的兴趣的一部分，我们希望开发出基于激进的基于基于碱的基础的新入口。富有价格廉价，无毒且具有高功能群的耐受性，有机动物已重新获得化学界的浓厚兴趣，作为选择的试剂，以发展更多的选择性反应。烷基辛的一个特定特征是它们可以作为极性亲核试剂（carbanions）反应，或者同型锌基（锌原子自由基转移）转移到烷基自由基中。将两种类型的反应性结合在单一反应中的可能性使得最近的多组分基于自由基的方法是烷烃和炔烃的碳酸化方法。遵循相同的策略，我们设想一种基于一个过程的方法，即一种方法，在这种过程中，甲硅烷基自由基将增加碳碳三键，以产生一种vinylic自由基，从而通过经过锌原子自由基转移而将其还原性地锌。因此，预期产生的二丁二烯二聚体物种非常适合原位功能化。在第一个研究轴中，我们将考虑使用甲硅烷基试剂。将在考虑在考虑碱间添加和分子内添加之前，研究了将二龙取代硅单元和其能力转移锌组的能力的新的二莲基因试剂的制备。在第二个轴上，将探索使用甲硅烷基自由基前体和二甲基二酮试剂的组合反应，主要集中在分子内转化上。最后，将探讨项目的第三部分，将使用1-硅烷-2-Zincio烷烃作为顺序碳碳键形成金属催化的交叉偶联反应的合作伙伴。