Schmidt reaction of 4-substituted adamantanones

Duddeck, H.; Brosch, Dino; Koppetsch, Gudrun

doi:10.1016/s0040-4020(01)91395-x

Cited by 6 publications

(1 citation statement)

References 12 publications

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“…As shown in Table , the syn -7-Cl ketone 16 (entry 3) and anti -7-Cl ketone 28 (entry 7) give only 4−5% 2-azalactams 18 and 30 , and the anti -7-Br ketone 31 (entry 8) gives no 2-azalactam 33 . The relatively large amounts of cleavage products observed during Schmidt reactions of anti -7-Cl ketone 28 and anti -7-Br ketone 31 can be rationalized by the speculative suggestion that an electron-withdrawing inductive effect, which facilitates isolation of BH migrated 2-azalactams 43 for the other 7-substituted examples of Table , is counterbalanced by anchimeric assistance of BH cleavage by anti -7-Br or anti -7-Cl substituents, as shown by 47 …”

Section: Discussionmentioning

confidence: 99%

Regioselective Functionalization. 6.¹ Migratory Preferences in Hydroxylamine-O-sulfonic Acid and Schmidt Rearrangements of 7-Substituted Norcamphors

Krow

Cheung

et al. 1996

J. Org. Chem.

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Hydroxylamine-O-sulfonic acid reacted with syn-7-X- and anti-7-Y-substituted norcamphor derivatives [X = H, OMe, Cl, Br, OTos; Y = H, COOMe, Cl, Br, Tos, COOMe(5-exo-Br)], to give solely bridgehead migrated 2-azalactams, except for minor amounts of methylene migrated 3-azalactams from norcamphor (1) and the syn-7-Br ketone 19. Schmidt reactions of the same ketones provided varying mixtures of methylene and bridgehead migrated lactams, except for norcamphor (1) and anti-7-Br ketone 31, which provided solely 3-azalactams. Significant ratios (>0.4) of bridgehead migration to cleavage products were observed in the Schmidt reactions only with 7-OTos ketones 22 and 24 with exo-5-bromo-anti-7-methoxycarbonyl ketone 37. The Schmidt rearrangements most likely involve iminodiazonium ion intermediates in light of the large amounts of cleavage observed relative to lactam formation and the insensitivity of methylene migration to the substituent size in the reactions of syn-7-substituted norcamphors.

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Section: Discussionmentioning

confidence: 99%

Regioselective Functionalization. 6.¹ Migratory Preferences in Hydroxylamine-O-sulfonic Acid and Schmidt Rearrangements of 7-Substituted Norcamphors

Krow

Cheung

et al. 1996

J. Org. Chem.

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The Schmidt Reaction

et al. 2012

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The classical form of the Schmidt reaction involves the reaction of a carbon‐centered electrophile with hydrazoic acid with loss of nitrogen, usually with a rearrangement that forms a new carbon‐nitrogen bond. Although the conversion of a ketone into an amide is the most commonly used variation, mechanistically related versions utilize an aldehyde, acid, or a carbocation generated from an alkene or alcohol as the electrophilic component. In recent years, the definition of the Schmidt reaction has been modified to include analogous reactions in which the hydrazoic acid is replaced by an alkyl azide, promoted by Lewis acids. The use of an alkyl azide uniquely permits the formulation of intramolecular Schmidt reactions of the azide with a carbonyl or carbocationic electrophile.

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C

1997

Reaktionen Der Organischen Chemie

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Schmidt reaction of 4-substituted adamantanones

Cited by 6 publications

References 12 publications

Regioselective Functionalization. 6.¹ Migratory Preferences in Hydroxylamine-O-sulfonic Acid and Schmidt Rearrangements of 7-Substituted Norcamphors

Regioselective Functionalization. 6.¹ Migratory Preferences in Hydroxylamine-O-sulfonic Acid and Schmidt Rearrangements of 7-Substituted Norcamphors

The Schmidt Reaction

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Schmidt reaction of 4-substituted adamantanones

Cited by 6 publications

References 12 publications

Regioselective Functionalization. 6.1 Migratory Preferences in Hydroxylamine-O-sulfonic Acid and Schmidt Rearrangements of 7-Substituted Norcamphors

Regioselective Functionalization. 6.1 Migratory Preferences in Hydroxylamine-O-sulfonic Acid and Schmidt Rearrangements of 7-Substituted Norcamphors

The Schmidt Reaction

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Regioselective Functionalization. 6.¹ Migratory Preferences in Hydroxylamine-O-sulfonic Acid and Schmidt Rearrangements of 7-Substituted Norcamphors

Regioselective Functionalization. 6.¹ Migratory Preferences in Hydroxylamine-O-sulfonic Acid and Schmidt Rearrangements of 7-Substituted Norcamphors