The mechanism of the barton reaction

Barton, D. H. R.; Hesse, Robert H.; Pechet, Maurice M.; Smith, Lauren C.

doi:10.1039/p19790001159

Cited by 54 publications

(20 citation statements)

References 3 publications

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“…In a detailed mechanistic study of the widely used Barton reaction, HNO has been proposed to occur as a reaction intermediate [26]. In the photolysis of e.g.…”

Section: Nomentioning

confidence: 99%

HNO, an Intermediate in (Light‐induced) Rearrangement Reactions of Nitrosooxy Compounds and Nitrosamines

Müller

Murata

Nonella

et al. 1984

Helvetica Chimica Acta

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IR‐spectroscopic investigations of light‐induced rearrangement reactions of nitrosooxymethane (CH3ONO3), nitrosooxyethane (CH3CH2ONO) and N,N‐dimethylnitrosamine ((CH3)2NNO) in low‐temperature rare‐gas matrices have established that these molecules are transformed in two photolysis steps to the previously unknown C‐nitroso compounds nitrosomethanol (CH2(OH)(NO)), 1‐nitrosoethanol (CH3CH(OH)(NO)), and methyl(nitrosomethyl)amine CH2(NO)(NH)(CH3). Evidence for a similar rearrangement reaction has been advanced for N‐Nitrosopyrrolidine which is converted to C‐nitrosopyrrolidine . The matrix‐isolation technique in combination with wavelength‐selective irradiation allowed to trap and characterize an intermediate of rearrangement which revealed to be nitroxyl (HNO) complex (CH2…HNO, CH3CHO…HNO, CH3N = CH2…HNO, and ). Since these findings have a close resemblance with rearrangement reactions of more complex nitrosooxy compounds, nitrosamines, or nitrosohydrazines used in organic synthesis, it is suggested that also in these reactions nitroxyl is present as an intermediate species.

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“…In a detailed mechanistic study of the widely used Barton reaction, HNO has been proposed to occur as a reaction intermediate [26]. In the photolysis of e.g.…”

Section: Nomentioning

confidence: 99%

HNO, an Intermediate in (Light‐induced) Rearrangement Reactions of Nitrosooxy Compounds and Nitrosamines

Müller

Murata

Nonella

et al. 1984

Helvetica Chimica Acta

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“…On irradiation with UV light in an O 2 -saturated benzene solution, a-nitrite 14 gave rise to the projected nitrate 15, albeit in very low yield (10%; see Scheme 2). These conditions also afforded 10% of the aldehyde 16 and 18% of the free alcohol 12 [20]. The b-nitrite 17 behaved ± to our surprise (vide infra) ± similarly under identical reaction conditions, providing the corresponding nitrate 18 (9%), aldehyde 19 (19%), and alcohol 13 (22%; compounds not shown).…”

mentioning

confidence: 73%

Synthesis of Cytostatic Tetradecacyclic Pyrazines and a Novel Reduction-Oxidation Sequence for Spiroketal Opening in Sapogenins

Bäsler¹,

Brunck

Jautelat³

et al. 2000

HCA

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“…The photochemical and thermochemical decomposition of alkyl nitrites first leads to homolysis of the O-NO bond (the homolytic bond dissociation energies range between 150-170 kJ/mol) followed by either H-abstraction in the case of straight-chain nitrites or ring opening for cyclic nitrites [63][64][65][66][67]. Due to the high electronegativity of O, the N-atom exhibit high electron deficiency, rendering them highly susceptible to nucleophilic attack by common nucleophiles (amines, thiols, carbanions), leading to NO + transfer in the so called transnitrosation processes which are very often in solution.…”

Section: Transfer Of ·No / No + Groupsmentioning

confidence: 99%

Cyclodextrins in Nitrosation Chemistry: New Insights of the NO-Transfer Processes

Iglesias

2005

MROC

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The chemistry of nitroso compounds has received considerable attention from several directions in recent years. This review will focus on describing the practical aspects, and current and potential applications of cyclodextrins in mechanistic studies of NO-transfer processes. The first section describes some physicochemical aspects of aqueous cyclodextrin solutions that are of crucial importance in relation to mechanistic studies. The next section analyses all types of information that can be obtained from different nitrosation reaction patterns either in acid or basic media, by paying special attention to the nitrosatable substrates and nitrosating agents. Relevant aspects concerning the biological activity of nitroso compounds is also included. The last section covers a detailed analysis of the effects of cyclodextrins on reactions undergone by nitroso compounds, such as hydrolysis or NO-transfer, as well as on reactions that produce nitroso compounds.

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The mechanism of the barton reaction

Cited by 54 publications

References 3 publications

HNO, an Intermediate in (Light‐induced) Rearrangement Reactions of Nitrosooxy Compounds and Nitrosamines

HNO, an Intermediate in (Light‐induced) Rearrangement Reactions of Nitrosooxy Compounds and Nitrosamines

Synthesis of Cytostatic Tetradecacyclic Pyrazines and a Novel Reduction-Oxidation Sequence for Spiroketal Opening in Sapogenins

Cyclodextrins in Nitrosation Chemistry: New Insights of the NO-Transfer Processes

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