NAZAROV CYCLIZATION REACTION
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(Redirected from Nazarov cyclization)
A 'Nazarov cyclization' is an organic reaction converting a divinylketone into a cyclopentenone under the influence of a Brønsted acid such as sulfuric acid or a Lewis acid such aluminum chloride [1]. The key intermediate in this reaction is a 'hydroxypentadienyl cation' and the key reaction step is a thermally allowed electrocyclic ring closure which in accordance with the Woodward-Hoffmann rules as a 4n π system is conrotatory.
The reaction was first reported by I.N. Nazarov in 1949.
The reaction mechanism for this reaction is outlined in ''scheme 2''. Divinylketone '1' is protonated with a proton donor to the pentadienyl cation '2' in which a positive charge is delocalized over 6 positions, a hybrid of 4 mesomers '2a' to '2d'. An electrocyclic ring closure takes place to the cyclopentenyl cation '3' and after an elimination reaction the proton is released again. The enol '4' rearranges to the ketone tautomer '5'.
In one study the Nazarov cyclization is paired with a Michael reaction [2]. In this tandem reaction (''scheme 3'') the iridium catalyst is required for both conversions: it acts as the Lewis acid in the Nazarov cyclization and in the next step the nitro group of nitrostyrene first coordinates to iridium in a ligand exchange with the carbonyl ester oxygen atom before the actual Michael addition takes place to the opposite face of the methoxybenzene group.
In an extension any pentadienyl cation regardless of its origin is capable of bringing about Nazarov reaction. In one study this species is obtained from an alkenyl-substituted dihalocyclopropane [3] [4]:
★ Nazarov cyclization in Organic Syntheses, Vol. 83, p.49 ('2005') Article.
★ Nazarov Cyclization @organic-chemistry.org Link
1. ''Named Organic Reactions'', 2nd Edition, Thomas Laue and Andreas Plagens, John Wiley & Sons: Chichester, England, New York, '2005'. 320 pp. ISBN 0-470-01041-X
2. ''Tandem Nazarov Cyclization-Michael Addition Sequence Catalyzed by an Ir(III) Complex'' Mesfin Janka, Wei He, Inga E. Haedicke, Frank R. Fronczek, Alison J. Frontier, and Richard Eisenberg J. Am. Chem. Soc.; '2006'; 128(16) pp 5312 - 5313; Graphical abstract
3. ''A New Approach to the Nazarov Reaction via Sequential Electrocyclic Ring Opening and Ring Closure'' Tina N. Grant and F. G. West J. Am. Chem. Soc.; '2006'; 128(29) pp 9348 - 9349; (Communication)
4. The silyl enol ether ''2-triisopropylsilyloxydiene'' '1' reacts with dichlorocarbene and a phase transfer catalyst to the dichlorocyclopropane '2'. Reaction with silver tetrafluoroborate of '2' strips a chlorine anion forming a cyclopanyl cation '3a' which rearranges to a cyclopropenyl cation '3b' and onwards to the Nazarov adduct '3c'. Proton elimination ('3d') and desilylation gives the cyclopentadienone '4'
A 'Nazarov cyclization' is an organic reaction converting a divinylketone into a cyclopentenone under the influence of a Brønsted acid such as sulfuric acid or a Lewis acid such aluminum chloride [1]. The key intermediate in this reaction is a 'hydroxypentadienyl cation' and the key reaction step is a thermally allowed electrocyclic ring closure which in accordance with the Woodward-Hoffmann rules as a 4n π system is conrotatory.
Scheme 1. Nazarov cyclization
The reaction was first reported by I.N. Nazarov in 1949.
| Contents |
| Mechanism |
| Scope |
| External links |
| References |
Mechanism
The reaction mechanism for this reaction is outlined in ''scheme 2''. Divinylketone '1' is protonated with a proton donor to the pentadienyl cation '2' in which a positive charge is delocalized over 6 positions, a hybrid of 4 mesomers '2a' to '2d'. An electrocyclic ring closure takes place to the cyclopentenyl cation '3' and after an elimination reaction the proton is released again. The enol '4' rearranges to the ketone tautomer '5'.
Scheme 2. Nazarov reaction mechanism
Scope
In one study the Nazarov cyclization is paired with a Michael reaction [2]. In this tandem reaction (''scheme 3'') the iridium catalyst is required for both conversions: it acts as the Lewis acid in the Nazarov cyclization and in the next step the nitro group of nitrostyrene first coordinates to iridium in a ligand exchange with the carbonyl ester oxygen atom before the actual Michael addition takes place to the opposite face of the methoxybenzene group.
Scheme 3. Nazarov-Michael tandem (Ph = phenyl)
In an extension any pentadienyl cation regardless of its origin is capable of bringing about Nazarov reaction. In one study this species is obtained from an alkenyl-substituted dihalocyclopropane [3] [4]:
Scheme 4. Nazarov variation
External links
★ Nazarov cyclization in Organic Syntheses, Vol. 83, p.49 ('2005') Article.
★ Nazarov Cyclization @organic-chemistry.org Link
References
1. ''Named Organic Reactions'', 2nd Edition, Thomas Laue and Andreas Plagens, John Wiley & Sons: Chichester, England, New York, '2005'. 320 pp. ISBN 0-470-01041-X
2. ''Tandem Nazarov Cyclization-Michael Addition Sequence Catalyzed by an Ir(III) Complex'' Mesfin Janka, Wei He, Inga E. Haedicke, Frank R. Fronczek, Alison J. Frontier, and Richard Eisenberg J. Am. Chem. Soc.; '2006'; 128(16) pp 5312 - 5313; Graphical abstract
3. ''A New Approach to the Nazarov Reaction via Sequential Electrocyclic Ring Opening and Ring Closure'' Tina N. Grant and F. G. West J. Am. Chem. Soc.; '2006'; 128(29) pp 9348 - 9349; (Communication)
4. The silyl enol ether ''2-triisopropylsilyloxydiene'' '1' reacts with dichlorocarbene and a phase transfer catalyst to the dichlorocyclopropane '2'. Reaction with silver tetrafluoroborate of '2' strips a chlorine anion forming a cyclopanyl cation '3a' which rearranges to a cyclopropenyl cation '3b' and onwards to the Nazarov adduct '3c'. Proton elimination ('3d') and desilylation gives the cyclopentadienone '4'
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