Selective synthesis and reactivity expansion of α,β-unsaturated geminal diazides

Chen, Chen; Ge, Jun; He, Ling

doi:10.1039/d2qo00008c

Cited by 3 publications

(2 citation statements)

References 33 publications

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“…Due to there being a range of available methods, geminal diazides derived from aldehydes are broadly accessible. 81 82 83 While studies on the reactivity of such diazides are still rare, a few interesting reactions with diazides derived from α,β-unsaturated aldehydes were recently disclosed. As summarized in Scheme 41 , the diazide 83 behaves mostly like a synthetic equivalent of a N , N -acetal: Single and double substitution is possible, as is elimination to imines and oxidation to nitriles.…”

Section: Reactivities Of Geminal Diazidesmentioning

confidence: 99%

“…He and co-workers have studied the reactivity of geminal diazides with the diazido group at an allylic position. 83 It was shown that double substitution was possible in the presence of Cu(OTf) 2 as a Lewis acid catalyst (Scheme 44 ). Diazides 94 reacted with an excess of electron-rich pyrroles (or furans) to give the bis(heterocyclo)methylene derivatives 95 .…”

Section: Reactivities Of Geminal Diazidesmentioning

confidence: 99%

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Reactions with Geminal Diazides: Long Known, Full of Surprises, and New Opportunities

Kirsch¹,

Bensberg²

2022

Synthesis

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Geminal diazides are uncommon yet powerful tools in organic synthesis. The chemistry of this class of functional compounds is characterized by quite unusual reactivities, including fragmentations and degradations, along with known reactions of organic azides. This Short Review highlights the major reactivities of various structural units having geminal diazido moieties, and provides an overview on the synthetic opportunities of such compounds.1 Introduction2 Preparation of Geminal Diazides3 Reactivities of Geminal Diazides3.1 α,α-Diazido Carbonyls3.2 1,3-Diketones3.3 Diazidated β-Ketoesters3.4 Diazidated Malonates3.5 Diazidated Malonamides3.6 Miscellaneous Geminal Diazides4 Conclusion

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Section: Reactivities Of Geminal Diazidesmentioning

confidence: 99%

Section: Reactivities Of Geminal Diazidesmentioning

confidence: 99%

Reactions with Geminal Diazides: Long Known, Full of Surprises, and New Opportunities

Kirsch¹,

Bensberg²

2022

Synthesis

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Ir‐Catalyzed Cascade Reaction Promotes the Formation of Geometrically Selective Enones from Bis‐allyl Alcohols

et al. 2022

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Enone compounds are well-known as useful building blocks that can be converted into a variety of valuable compounds. This study describes a synthetic method to synthesize Eselective or multi-substituted enones by an Ir-catalyzed cascade reaction under reducing conditions. We found that the cascade reaction, including reduction/isomerization/dehydration, pro-ceeds by treating bis-allyl alcohol with Crabtree's catalyst in a hydrogen atmosphere, which forms the desired product with high diastereoselectivity. We investigated acceptable catalysts to the reaction and the synthesis of enone using di-, tri-and tetrasubstituted olefin substrates. Additionally, the given results suggested a hypothesis of reaction mechanism.

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Di- and polyazides. Synthesis, chemical transformations and practical applications

Tsyrenova,

Lemport,

Nenajdenko

2023

RUSS CHEM REV

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В последние годы активно развивается химия органических ди- и полиазидов. Методы синтеза 1,1-диазидов и 1,2-диазидов разнообразны и включают стехиометрические, каталитические, фотохимические и электрохимические подходы. Реакционная способность этих соединений очень высока, что отражает широкий круг их реакций — от термических превращений до "клик"-химии. Особого внимания заслуживают процессы, в которых одна из азидных групп вступает в реакцию внутримолекулярной циклизации, при этом вторая азидная группа остается незатронутой, что позволяет проводить дальнейшие химические трансформации с ее участием. Три- и полиазиды исследуют в качестве прекурсоров для создания высокоэнергетических веществ и синтеза высокомолекулярных соединений. Настоящий обзор посвящен способам получения и особенностям химических трансформаций органических соединений, которые содержат две и более азидные группы. Рассмотрены алифатические, ароматические и гетероароматические диазиды. Показаны специфические превращения, характерные для геминальных и вицинальных диазидов и отличающиеся от реакций моноазидов. Освещены некоторые примеры практического применения ди-, три- и полиазидов. <br> Библиография — 355 ссылок.

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Selective synthesis and reactivity expansion of α,β-unsaturated geminal diazides

Abstract: α,β-Unsaturated gem-diazides were selectively obtained catalyzed by Yb(TfO)3 using α,β-unsaturated aldehydes as substrates and TMSN3 as a nitrogen source under mild and simple conditions in moderate yields without Schmidt and allylic rearrangement.

Cited by 3 publications

References 33 publications

Reactions with Geminal Diazides: Long Known, Full of Surprises, and New Opportunities

Reactions with Geminal Diazides: Long Known, Full of Surprises, and New Opportunities

Ir‐Catalyzed Cascade Reaction Promotes the Formation of Geometrically Selective Enones from Bis‐allyl Alcohols

Di- and polyazides. Synthesis, chemical transformations and practical applications

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