摘要：YannickBrägger†, Ann-Sophie K. Paschke†, Nima Nasiri, Bence B. Botlik, FrancescoFelician, BillMorandi*

转自：康龙化成

Oxidative Amination by Nitrogen Atom Insertion into Carbon-carbon Double Bonds

YannickBrägger†, Ann-Sophie K. Paschke†, Nima Nasiri, Bence B. Botlik, FrancescoFelician, BillMorandi*

Laboratoriumfür Organische Chemie, ETH Zürich, Zürich, Switzerland.

†Theseauthors contributed equally to this work

—Science 2025, 10.1126/science.adq4980

Recommended by Rui Jin _ MC5

KEYWORDS: carbon-carbon double bonds cleavage, oxidative amination, nitrogen insertion, skeletalediting (反应类型), C(sp)≡N,C(sp2)=N, C(sp3)-N (成键类型),alkenes, ammonium carbamate, PIFA (原料), nitriles, amidines (产物), HFIP,aza-allenium intermediate, aza-Beckmannrearrangement (其他)

ABSTRACT: The synthesis of nitrogen-containing molecules through carbon–nitrogen (C–N) bond formation is critical for the discovery and preparation of medicines, agrochemicals, and materials. Here, Bill Morandi et al. report the direct insertion of a nitrogen atom into unactivated carbon-carbon double bonds to access aza-alleniumintermediates, which can be converted either into nitriles or amidine products, depending on the initial alkene substitution pattern. This operationally simple and highly functionally compatible reaction works on a wide range of unactivatedalkenes. PIFA, a commercially available and inexpensive hypervalent iodine reagent, is key to this reactivity. Our mechanistic proposal is supported by chemical trapping experiments, which concomitantly demonstrate the utility of our method to access valuable N-heterocycles. Additionally, our method can be used as a general strategy for synthesizing amides and amines, as well as 15N-labeled molecules.

Background and this work

Proposed mechanism

Substrate scope: linear alkenes (selectedexamples)

Substrate scope: branched alkenes (selected examples)

15N labeling studies

Insummary, BillMorandi et al.have developed an oxidative amination reaction, inwhich linearalkenes are cleaved to nitriles and branched alkenes are transformed intoamidines. Weposit a mechanism involving nitrogen atom insertion intothe C(sp2)–C(sp2) bond of unactivated alkenes, taking advantage of transient aza-allenium intermediates ina synthetically useful application. The reaction setup is operationally simple,requiring no exclusion of air or moisture, and is compatible with manyfunctionalities. In a broader context, this study demonstrates that nitrogeninsertion into alkenes can enable the formation of aza-alleniumspecies as reactive nitrogen-containing intermediates with broad syntheticutility and outstanding potential for downstream diversification, openingavenues for the discovery and preparation of important nitrogen-containingproducts.

苏黎世联邦理工学院BillMorandi教授团队开发了一种C=C双键氧化胺化反应，其中线性烯烃被裂解为腈类，而支链烯烃被转化为脒类。作者提出了一种机理，氮原子插入未活化烯烃的C=C双键中形成瞬态氮杂联烯基中间体，进而转化为产物。该反应设置操作简单，无需排除空气或水反应分，并且与许多官能团兼容。这项研究表明，将氮原子插入烯烃中形成氮杂联烯可作为活性含氮中间体，具有广泛的合成应用前景，为发现和制备重要的含氮产品开辟了途径。

来源：新浪财经