Hydrogen-bond activation enables aziridination of unactivated olefins with simple iminoiodinanes

IF 2.2 4区化学 Q2 CHEMISTRY, ORGANIC

Beilstein Journal of Organic Chemistry Pub Date : 2024-09-11 DOI:10.3762/bjoc.20.197

Phong Thai, Lauv Patel, Diyasha Manna, David C. Powers

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Abstract

Iminoiodinanes comprise a class of hypervalent iodine reagents that is often encountered in nitrogen-group transfer (NGT) catalysis. In general, transition metal catalysts are required to effect efficient NGT to unactivated olefins because iminoiodinanes are insufficiently electrophilic to engage in direct aziridination chemistry. Here, we demonstrate that 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) activates N-arylsulfonamide-derived iminoiodinanes for the metal-free aziridination of unactivated olefins. ¹H NMR and cyclic voltammetry (CV) studies indicate that hydrogen-bonding between HFIP and the iminoiodinane generates an oxidant capable of direct NGT to unactivated olefins. Stereochemical scrambling during aziridination of 1,2-disubstituted olefins is observed and interpreted as evidence that aziridination proceeds via a carbocation intermediate that subsequently cyclizes. These results demonstrate a simple method for activating iminoiodinane reagents, provide analysis of the extent of activation achieved by H-bonding, and indicate the potential for chemical non-innocence of fluorinated alcohol solvents in NGT catalysis.

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Beilstein J. Org. Chem. 2024, 20, 2305–2312. doi:10.3762/bjoc.20.197

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氢键活化使未活化的烯烃与简单的亚氨基碘烷发生氮丙啶化反应

摘要亚氨基碘烷是氮基转移（NGT）催化中经常遇到的一类高价碘试剂。一般来说，需要使用过渡金属催化剂才能对未活化的烯烃进行有效的氮基转移，因为亚氨基碘烷的亲电性不足，无法直接进行叠氮化化学反应。在这里，我们证明了 1,1,1,3,3,3- 六氟异丙醇（HFIP）可以激活 N-芳基磺酰胺衍生的亚氨基碘烷，从而对未活化的烯烃进行无金属氮丙啶化反应。1H NMR 和循环伏安法 (CV) 研究表明，HFIP 和亚氨基碘烷之间的氢键作用产生了一种氧化剂，能够直接对未活化的烯烃进行 NGT。在 1,2-二取代烯烃的叠氮化过程中观察到了立体化学混杂现象，并将其解释为叠氮化是通过随后环化的碳位中间体进行的。这些结果展示了一种活化亚氨基碘烷试剂的简单方法，提供了对通过 H 键实现的活化程度的分析，并指出了氟化醇溶剂在 NGT 催化中的化学非抑制潜力。Chem.2024, 20, 2305–2312. doi:10.3762/bjoc.20.197

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来源期刊

Beilstein Journal of Organic Chemistry 化学-有机化学

CiteScore

4.90

自引率

3.70%

发文量

167

审稿时长

1.4 months

期刊介绍： The Beilstein Journal of Organic Chemistry is an international, peer-reviewed, Open Access journal. It provides a unique platform for rapid publication without any charges (free for author and reader) – Platinum Open Access. The content is freely accessible 365 days a year to any user worldwide. Articles are available online immediately upon publication and are publicly archived in all major repositories. In addition, it provides a platform for publishing thematic issues (theme-based collections of articles) on topical issues in organic chemistry. The journal publishes high quality research and reviews in all areas of organic chemistry, including organic synthesis, organic reactions, natural product chemistry, structural investigations, supramolecular chemistry and chemical biology.

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