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Reaction mechanism
The Corey–Fuchs reaction, also known as the Ramirez–Corey– Corey–Fuchs reaction
See also Fuchs reaction, is a series of chemical reactions designed to Named after Elias James Corey
[1][2][3]
transform an aldehyde into an alkyne. The formation of the Philip L. Fuchs
References
1,1-dibromoolefins via phosphine-dibromomethylenes was Reaction type Substitution reaction
External links originally discovered by Desai, McKelvie and Ramirez.[4] The Identifiers

second step of the reaction to convert dibromoolefins to alkynes Organic Chemistry corey-fuchs-reaction
Portal
is known as Fritsch–Buttenberg–Wiechell rearrangement. The
RSC ontology ID RXNO:0000146
overall combined transformation of an aldehyde to an alkyne by
this method is named after its developers, American chemists
Elias James Corey and Philip L. Fuchs.

CBr4
Br Br1)BuLi

R H РРИз 2)H20 R
R'

By suitable choice of base, it is often possible to stop the reaction at the 1-bromoalkyne, a useful functional
group for further transformation.

Reaction mechanism [ edit ]

The Corey–Fuchs reaction is based on a special case of the Wittig reaction, where two equivalents of
triphenylphosphine are used with carbon tetrabromide to produce the triphenylphosphine-dibromomethylene
ylide.

Вг
Br Br
Br.
PhiP-Br PPhz
Br
Br Br
Br Br Br Br

Br4
PPIe Br.

.C. Br
C= -PPh,
Br Br

-:PPh3

This ylide undergoes a Wittig Reaction when exposed to an aldehyde. Alternatively, using a ketone generates a
gem-dibromoalkene.

Br Br. BroC •PPh3 Br. Br

=PPh3
BI Br
H°
HI

The second part of the reaction converts the isolable gem-dibromoalkene intermediate to the alkyne.
Deuterium-labelling studies show that this step proceeds through a carbene mechanism. Lithium-Bromide
exchange is followed by α-elimination to afford the carbene. 1,2-shift then affords the deuterium-labelled
terminal alkyne.[1] The 50% H-incorporation could be explained by deprotonation of the (acidic) terminal
deuterium with excess BuLi.

Br Bin
3и-і aeliminaion 2-shi

nexane
MeC -13"Ctori MeO MeO MeO

92%D 50%D

See also [ edit ]

Appel reaction
Fritsch-Buttenberg-Wiechell rearrangement
Seyferth-Gilbert homologation
Wittig reaction

References [ edit ]

1. ^ Sahu, Bichismita; Muruganantham, Rajendran; Namboothiri, Irishi N. N. (2007). "Synthetic and Mechanistic
Investigations on the Rearrangement of 2,3-Unsaturated 1,4-Bis(alkylidene)carbenes to Enediynes" . European
Journal of Organic Chemistry. 2007 (15): 2477–2489. doi:10.1002/ejoc.200601137 . ISSN 1434-193X .

1. ^ Corey, E. J.; Fuchs, P. L. Tetrahedron Lett. 1972, 13, 3769–3772. doi:10.1016/S0040-4039(01)94157-7

2. ^ Mori, M.; Tonogaki, K.; Kinoshita, A. Organic Syntheses, Vol. 81, p. 1 (2005). (Article Archived 2011-05-14
at the Wayback Machine)
3. ^ Marshall, J. A.; Yanik, M. M.; Adams, N. D.; Ellis, K. C.; Chobanian, H. R. Organic Syntheses, Vol. 81, p. 157
(2005). (Article Archived 2011-05-14 at the Wayback Machine)
4. ^ N. B. Desai, N. McKelvie, F. Ramirez JACS, Vol. 84, p. 1745-1747 (1962). doi:10.1021/ja00868a057

External links [ edit ]

Corey-Fuchs Alkyne Synthesis

V·T·E Alkynes [show]

V·T·E Topics in organic reactions [show]

Categories: Substitution reactions Carbon-carbon bond forming reactions Rearrangement reactions

Name reactions

This page was last edited on 27 October 2022, at 19:28 (UTC).

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