Ramberg–Bäcklund reaction

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Ramberg–Bäcklund reaction
Named after
Birger Bäcklund
Reaction type Rearrangement reaction
Identifiers
Organic Chemistry Portal ramberg-baecklund-reaction
RSC ontology ID RXNO:0000094

The Ramberg–Bäcklund reaction is an organic reaction converting an α-halo sulfone into an alkene in presence of a base with extrusion of sulfur dioxide.[1] The reaction is named after the two Swedish chemists Ludwig Ramberg and Birger Bäcklund. The carbanion formed by deprotonation gives an unstable episulfone that decomposes with elimination of sulfur dioxide. This elimination step is considered to be a concerted cheletropic extrusion.[citation needed]

Scheme 1. The Ramberg–Bäcklund reaction
Scheme 1. The Ramberg–Bäcklund reaction

The overall transformation is the conversion of the carbon–sulfur bonds to a carbon–carbon double bond. The original procedure involved halogenation of a

oxidation, which is normally done with a peroxy acid, halogenation is done under basic conditions by use of dibromodifluoromethane for the halogen transfer step. [2]
This method was used to synthesize 1,8-diphenyl-1,3,5,7-octatetraene.

Scheme 2. Using the Ramberg–Bäcklund reaction to synthesize 1,8-diphenyl-1,3,5,7-octatetraene
Scheme 2. Using the Ramberg–Bäcklund reaction to synthesize 1,8-diphenyl-1,3,5,7-octatetraene

Applications

The Ramberg–Bäcklund reaction has several applications. Due to the nature of elimination, it can be applied to both small rings [3],

Scheme 3. Small-ring application of the Ramberg–Bäcklund reaction
Scheme 3. Small-ring application of the Ramberg–Bäcklund reaction

and large rings containing a double bond [4].

Scheme 4. Small-ring application of the Ramberg–Bäcklund reaction
Scheme 4. Small-ring application of the Ramberg–Bäcklund reaction

This reaction type gives access to 1,2-dimethylenecyclohexane[5]

Scheme 5. Ramberg–Bäcklund synthesis of dimethylene-cyclohexane
Scheme 5. Ramberg–Bäcklund synthesis of dimethylene-cyclohexane

and the epoxide variation [6] access to allyl alcohols.

oxidation of a sulfamide generates a azo compound.[1]

Substrates

The necessary α-halo sulfones are accessible through oxidation of the corresponding α-halo sulfides with peracids such as

meta-chloroperbenzoic acid; oxidation of sulfides takes place selectively in the presence of alkenes and alcohols. α-Halo sulfides may in turn be synthesized through the treatment of sulfides with halogen electrophiles such as N-chlorosuccinimide or N-bromosuccinimide.[8]

Mechanism

The

cis isomer and trans isomer are usually obtained.[9]

The Favorskii rearrangement and the Eschenmoser sulfide contraction are conceptually related reactions.

References

  1. ^ Ohme, R.; Preuschhof, H.; Heyne, H.-U. (1988). "Azoethane". Organic Syntheses; Collected Volumes, vol. 6, p. 78.
  1. ISSN 0365-3781
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  7. ; Collected Volumes, vol. 8, p. 212.
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