Regioselective Intramolecular Allene Amidation Enabled by an EDA Complex*.
Regioselective Intramolecular Allene Amidation Enabled by an EDA Complex*.
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DOI：
10.1002/chem.202002533
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发表时间：
2020-11-02
期刊：
影响因子：
--
通讯作者：
Schomaker JM
中科院分区：
文献类型：
--
作者：
Liu L;Ward RM;Schomaker JM
向不饱和前体添加自由基是合成碳环和杂环有机结构单元的有力工具。最近出现的产生 N 中心自由基的温和方法重新激发了人们对利用这些反应性中间体进行高度区域选择性、化学选择性和立体选择性转化的兴趣。虽然氨基、亚氨基和酰胺基与烯烃和炔烃的加成已经得到充分研究，但对丙二烯的类似加成却很少。艾伦烯具有多种吸引人的特性，包括通过明智地选择前体或自由基源在三个不同位点进行选择性酰胺化的潜力、轴向到点手性转移的机会以及有效捕获乙烯基或烯丙基自由基中间体以使产品的功能多样化。在本文中，我们报道了酰胺基自由基与丙二烯的区域选择性加成，以提供一系列有价值的N-杂环支架。 N-中心自由基与丙二烯的区域控制加成是获得官能化杂环的尚未充分探索的机会。本手稿报告了我们对酰胺和氨基甲酸酯衍生的 N-自由基与丙二烯的分子内加成的初步研究。由初始 C-N 键形成产生的中间乙烯基自由基被各种亲电试剂捕获，形成新的 C-H、C-P、C-Se 和 C-X 键。
The addition of radicals to unsaturated precursors is a powerful tool for the synthesis of both carbo- and heterocyclic organic building blocks. The recent advent of mild ways to generate N-centered radicals has reignited interest in exploiting highly regio-, chemo-, and stereoselective transformations that employ these reactive intermediates. While the additions of aminyl, iminyl, and amidyl radicals to alkenes and alkynes have been well-studied, analogous additions to allenes are scarce. Allenes offer several attractive features, including potential for selective amidation at three distinct sites via judicious choice of precursor or radical source, the opportunity for axial-to-point chirality transfer, and productive trapping of vinyl or allyl radical intermediates to diversify functionality in the products. In this article, we report a regioselective addition of amidyl radicals to allenes to furnish an array of valuable N-heterocycle scaffolds. The regiocontrolled additions of N-centered radicals to allenes is an underexplored opportunity to access functionalized heterocycles. This manuscript reports our initial investigations into intramolecular additions of amide- and carbamate-derived N-radicals to allenes. The intermediate vinyl radicals resulting from the initial C-N bond formation are trapped with various electrophiles to form new C-H, C-P, C-Se, and C-X bonds.
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影响因子：
4.3
作者：
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通讯作者：
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影响因子：
3.2
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1.8
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2.8
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通讯作者：
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