Nitrenium ions. VII. Synthesis and solvolysis of 4,7,7-trimethyl-2-chloro-2-azabicyclo[2.2.1]heptane

Gassman, Paul G.; Cryberg, Richard L.

doi:10.1021/ja01036a031

Cited by 23 publications

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“…The silver ion catalyzed rearrangements of azabicycloheptanes (23), the surprisingly rapid internal reaction of primary chloramines with olefinic double bonds discovered by Nagata and coworkers (24) and the silver ion catalyzed cycloaddition of unsaturated secondary chloramines described by Hobson and Riddell (25) present mechanistic problems that merit further study.…”

Section: Discussionmentioning

confidence: 99%

Reactions of Chloramines with Ag(0) and Ag(I) States

Edwards¹,

Vocelle²,

ApSimon³

1972

Can. J. Chem.

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Reactions of N-chloroazacyclooctane and N-chloroazacyclononane are described which give good yields of bicyclic amines. These are : ( a ) short chain homolytic reactions involvingneutralnitrogen radicals initiated by ferrous ion or metallic silver; ( b ) apparent homogeneous reactions involving silver ion and bases; ( c ) reactions using silver oxide suspension which also require added bases.Both rate and product composition for ( b ) and ( c ) are sensitive to oxygen indicating that they are homolytic processes, probably initiated by traces of silver metal. N o evidence for involvement of discrete nitrenium ions was found. However, reaction of N-chloroisoquinuclidine with silver ions has the character of a heterolytic process, giving products completely distinct from those from its homolytic decomposition. The addition of neutral piperidino radicals to styrene is described.On decrit les reactions du N-chloroazacycloactane et du N-chloroazacyclononane, qui donnent de bons rendements en amines bicycliques. Ce sont: ( a ) les reactions homolytiques de courtes chaines irnpliquant des radicaux azote tleulres inities par I'ion ferreux ou l'argent mttallique; ( b ) des rkactions homogenes apparentes impliquant I'ion argent et des bases; ( c ) des reactions utilisant une suspension d'oxyde d'argent impliquant aussi l'addition de bases.La vitesse et la composition du produit, dans les cas ( b ) et ( c ) sont sensibles a I'oxygene, indiquant que ce sont des proctdes homolytiques, initits probablement par des traces d'argent metalliques. On n'a pu prouver I'implication dans ces reactions des ions nitrenium. Toutefois, la reaction du N-chloroisoquinuclidine avec les ions argent possede le caractere d'un procede heterolytique, donnant des produits completement distincts de ceux provenant de sa decomposition homolytique. L'addition de radicaux tleutres piperidino au styrene est aussi decrite.

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Section: Discussionmentioning

confidence: 99%

Reactions of Chloramines with Ag(0) and Ag(I) States

Edwards¹,

Vocelle²,

ApSimon³

1972

Can. J. Chem.

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1,7,7-Trimethyl-3-azabicyclo[2.2.1]heptan-2-one

Collison

Boeckman

2008

Encyclopedia of Reagents for Organic Synthesis

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Hofmann‐Löffler‐Freytag Reaction

2010

Comprehensive Organic Name Reactions and Reagents

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The synthesis of pyrrolidine or piperidine derivatives by thermal or photochemical decomposition of the protonated aliphatic N ‐haloamines is generally known as Hofmann–Löffler–Freytag reaction. Many experimental evidences support the radical mechanism of this reaction, such as the initiation of the reaction by either photo‐irradiation or traditional radical initiators and the inhibition of reaction by oxygen. In this reaction, hydrogen abstraction is the chain‐propagating step. Presently, many other methods have been established to generated aminium radicals. This reaction has been extended to amidyl radical, sulfonamidyl radical, and other nitrogenous radicals. This reaction has been applied for the preparation of substituted pyrrolidines and piperidines.

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Nitrenium ions. VII. Synthesis and solvolysis of 4,7,7-trimethyl-2-chloro-2-azabicyclo[2.2.1]heptane

Cited by 23 publications

References 0 publications

Reactions of Chloramines with Ag(0) and Ag(I) States

Reactions of Chloramines with Ag(0) and Ag(I) States

1,7,7-Trimethyl-3-azabicyclo[2.2.1]heptan-2-one

Hofmann‐Löffler‐Freytag Reaction

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