Electrophilic Bond Insertion by Cationic Nitrogen

Lansbury, Peter T.; Colson, James G.; Mancuso, Norman R.

doi:10.1021/ja01077a037

Cited by 24 publications

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“…to two carbonyl groups and are expected to be shifted upfield with respect to the methine protons of compounds 2a and 2b. These values are consistent with literature values for lactams (10).…”

Section: The Absorptions Given Insupporting

confidence: 93%

The schmidt reaction on 3a,4,5,6‐tetrahydrosuccinimido[3,4‐b]‐acenaphthen‐10‐one and its alkylated derivatives

Campaigne¹,

Huffman²,

Yodice³

1981

Journal of Heterocyclic Chem

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The rearrangement of 3a,4,5,6‐tetrahydrosuccinimido[3,4‐b]acenaphthen‐10‐one and two methylated derivatives using Schmidt conditions is described. The ratio of the major product, 2,3,8,9‐tetrahydro‐3‐oxo‐1H‐benz[de]isoquinoline‐1,9a‐(7H)dicarboximide, to the minor product, 2,3,6,7‐tetrahydro‐3‐oxo‐4H‐benz[ij]‐isoquinoline‐4,4a‐(5H)dicarboximide, under different acidic conditions is given. The ratios of analogous products from the methylated derivatives are similar under similar conditions.

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Section: The Absorptions Given Insupporting

confidence: 93%

The schmidt reaction on 3a,4,5,6‐tetrahydrosuccinimido[3,4‐b]‐acenaphthen‐10‐one and its alkylated derivatives

Campaigne¹,

Huffman²,

Yodice³

1981

Journal of Heterocyclic Chem

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“…A survey of the relevant literature revealed a single example by Lansbury and co-workers who reported that 7-alkyl-1-indanone oximes undergo C−H bond insertion when treated with polyphosphoric acid at 130 °C . The authors speculated that a very strained system prevented the Beckmann rearrangement from occurring which led to the observed product via an alternate pathway.…”

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confidence: 99%

Novel Intramolecular Reactivity of Oximes: Synthesis of Cyclic and Spiro-Fused Imines

et al. 2007

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Under conventional heat (135-145 degrees C) or microwave irradiation and 1 equiv of acetic anhydride, ortho-substituted aryl-oximes undergo a novel sp3 C-H activated cyclization to produce the corresponding isoindoles, and aliphatic oximes afford the corresponding dihydropyrroles. The cyclization occurs with various substrates in good yield (46-82%) leading to unique spiro-fused and cyclic imines. An initial mechanistic investigation suggests the reaction occurs via a nitrenium or vinyl nitrene intermediate. [reaction: see text]

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TheBeckmann Reactions: Rearrangements, Elimination–Additions, Fragmentations, and Rearrangement–Cyclizations

Gawley

1988

Organic Reactions

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The Beckmann rearrangement, the acid‐mediated isomerization of oximes to amides, was discovered by Beckmann in 1886. As one of the oldest and most familiar transformations in organic chemistry, it has been reviewed several times. What has become known as the Beckmann fragmentation was in fact first observed by Wallach in 1889 but was not developed extensively until the 1960s. It has been referred to by several names over the years and has also been reviewed. The rearrangement cyclization is the intramolecular cyclization of a nitrilium ion generated by Beckmann rearrangement from an oxime. Within the context of an aromatic terminator, the process was first reported by Goldschmidt in 1895. Wallach reported the first case of an aliphatic terminator in 1901, although the reported structure was incorrect, and Perkin was apparently the first to observe a heteroatom terminator, but he also reported an incorrect structure. The process has been exploited only quite recently. This chapter is an update of these reactions, last reviewed in this series in 1960. Not covered are transformations that have been labeled Beckmann‐type reactions but are mechanistically unrelated. The most prominent of these is the so‐called photochemical Beckmann rearrangement, first observed by De Mayo in 1963 and discussed in a review several years ago. Worthy of mention, however, is the fact that many oximes that suffer fragmentation under acidic conditions undergo rearrangement when photolyzed. Throughout this chapter, the ( E ) and ( Z ) nomenclature is used to describe oxime geometry.

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Electrophilic Bond Insertion by Cationic Nitrogen

Cited by 24 publications

References 0 publications

The schmidt reaction on 3a,4,5,6‐tetrahydrosuccinimido[3,4‐b]‐acenaphthen‐10‐one and its alkylated derivatives

The schmidt reaction on 3a,4,5,6‐tetrahydrosuccinimido[3,4‐b]‐acenaphthen‐10‐one and its alkylated derivatives

Novel Intramolecular Reactivity of Oximes: Synthesis of Cyclic and Spiro-Fused Imines

TheBeckmann Reactions: Rearrangements, Elimination–Additions, Fragmentations, and Rearrangement–Cyclizations

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