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REVISTA BOLIVIANA DE QUMICA (Rev.Bol.Quim.

)
Bolivian Journal of Chemistry
Received 10 11 2015

Accepted 10 28 2015
Bravo et Vila

Vol. 32, No.4, pp. 82-89, Sep./Nov. 2015


32(4) 82-89, Sep./Nov. 2015
Published 11 11 2015
.

SYNTHESIS OF ALKENES FROM KETONES VIA ARYLSULPHONYLHYDRAZONES; MECHANISTIC VIEWS; THE ORGANIC CHEMISTRY
NOTEBOOK SERIES, A DIDACTICAL APPROACH, N 7
Jos A. Bravo1,*, Jos L. Vila2
1

Department of Chemistry, Laboratorio de Fitoqumica, Instituto de Investigaciones en Productos Naturales


IIPN, Universidad Mayor de San Andrs UMSA, P.O. Box 303, Calle Andrs Bello s/n, Ciudad Universitaria
Cota Cota, Phone 59122792238, La Paz, Bolivia, jabravo@umsa.bo

Department of Chemistry, Laboratorio de Sntesis y Hemisntesis, Instituto de Investigaciones en Productos


Naturales IIPN, Universidad Mayor de San Andrs UMSA, P.O. Box 303, Calle Andrs Bello s/n, Ciudad
Universitaria Cota Cota, Phone 59122795878, La Paz, Bolivia, joselu62@hotmail.com

Keywords: Organic Chemistry, Ketones, Arylsulphonylhydrazones, Alkenes, Mechanisms of


Reactions, W. Carruthers.
ABSTRACT
This is the seventh chapter in the series published by the same authors: The Organic Chemistry Notebook Series, a
Didactical Approach.
The aim of this series of studies is to help students to have a graphical view of organic synthesis reactions of
diverse nature. Here we describe the mechanistic views of the synthesis of alkenes from ketones via
arylsulphonylhydrazones. These methods employ aliphatic and alicyclic ketones with one -hydrogen, that react
along with toluene-p-sulphonylhydrazones and two equivalents of an alkyl-lithium or lithium diisopropylamide. The
mechanism views for the transformation of pinacolone into 3,3-dimethyl-1-butene are proposed. The formation of 3phenylpropene using phenylacetone is explained step by step. An approach is made on the obtaining of alkenes from
ketones using derived enol ethers or esters by means of reductive excision or by means of coupling with
organocuprates. We have used various series of reactions reviewed by W. Carruthers in Some modern methods of
organic synthesis, and we have proposed didactical and mechanistic views for them. This theme is included in the
chapter Formation of carbon-carbon double bonds in the text mentioned above. Spanish title: Sntesis de alquenos a partir
de cetonas via arilsulfonilhidrazonas; vistas mecansticas; De la serie: El cuaderno de notas de qumica orgnica, un enfoque didctico, N7.

*Corresponding author: joseabravo@outlook.com


INTRODUCTION
During master classes of organic chemistry it is possible to notice that students are confronted with a lack of
knowledge with regard to mechanisms. For instance, oxidation-reduction reactions which are among the most
commonly employed constitute a kind of black box for the students mind. A mechanistic approach of any kind of
reaction enhances the capacity of facing new reactions with respect to an understanding of all processes involved in
them, and also develops synthetic creativity. As academics we feel concerned with the didactical importance of
covering these needs in debutant students in organic synthesis. This, the synthesis of alkenes from ketones via
arylsulphonylhydrazones, is the seventh study in: The Organic Chemistry Notebook Series, a Didactical Approach
[1-6].
REACTIONS AND THEIR MECHANISTIC PROPOSALS, DISCUSSION
Aliphatic and alicyclic ketones with at least one hydrogen in are employed to synthesize alkenes [7]. The method
includes reaction of ketones with toluene-p-sulphonylhydrazones and the addition of two equiv of lithium
diisopropylamide or alkyl lithium [7-9]. Products present no changes in the carbon framework, and given the
adequate mild conditions; the less substituted alkene is obtained [7]. Pinacolone gives an only product: 3,3-dimethylDownloadable from: Revista Boliviana

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REVISTA BOLIVIANA DE QUMICA (Rev.Bol.Quim.)


Bolivian Journal of Chemistry
Received 10 11 2015

Accepted 10 28 2015
Bravo et Vila

Vol. 32, No.4, pp. 82-89, Sep./Nov. 2015


32(4) 82-89, Sep./Nov. 2015
Published 11 11 2015
.

1-butene [7]. See Fig. 1 and 2, and Fig. 3 for a mechanistic explanation. 3-phenylpropene is brought forth by
phenylacetone, however no styrene is present after reaction [7] (Fig. 1, 2 and Fig. 4).
(1) 2 equiv C4H9Li

C6H6
(2) H2O

NNHTos

'quantitative'

pinacolone

C6H5

(1) 2 equiv C4H9Li


C6H14-TMEDA

C6H5
O

C6H5

(2) D2O

NNHTos

D
(74%)

(Tos = pCH3C6H4SO2 ; TMEDA = tetramethylethylenediamine)

Figure 1. Alkenes (the less substituted) from ketones via arylsulphonylhidrazones; reviewed by W. Carruthers [7]

Various steps are applicable to the reaction. First, the anion 1 is formed by action of the first alkyl lithium [7]. Then
the second equivalent of alkyl lithium generates another charge and the dianion 2 appears. Localization of the
excessive charge in the carbanion of 2, leads to the fragmentation of the arylsulphonyl moiety [7]. The resulting
anionic diazo-alkene becomes a carbanion by means of excision of one molecule of gaseous nitrogen; the carbanion
makes a new covalence with one cation Lithium, the other one compensates the charge of the arylsulphonate [7]. The
yield can be improved by using tetramethylethylenediamine (TMEDA) [7] as solvent. TMEDA is the additive or
solvent necessary to obtain the less substituted alkene from an unsymmetrical ketone [7]. When an ethereal or
hydrocarbon solvent is used, the C=C bond occupies a position defined by the stereochemistry of the hydrazone [7].
The second abstraction of the a proton in 1, happens in a syn way to the ArSO2N(-)- [7,10].
Intermediate 3 can suffer interchange of the cation Li+ with H+ of the solvent (or an alternative source of
protons) or being substituted by another electrophile [7]. See Fig. 2 and Fig. 3.
R1

R1

R
O

C4H9Li

R1

N
NHSO2Ar

H
+
(-) Li
R2

R1
N
2

N(-) SO2Ar
Li+

H
2

R
N

C4H9Li

N(-)SO2Ar
Li+

H
R1

R
N

R1
3

(-)
N(-) SO2Ar
Li+ Li+

E+

R2

R1

CHR2
E

Li
N

(-)

SO2Ar
Li+

Figure 2. Alkenes (the less substituted) from ketones via arylsulphonylhidrazones; intermediates description; reviewed by W.
Carruthers [7]

In TMEDA, submitting the reaction to the adding of deuterium oxide is a way to deuterated alkenes (Fig. 1 and Fig.
4) [7]. 2-methylcyclohexanone (4, Fig. 5 and 6), gives rise to 2-deuterio-3-methyl cyclohexene, and octan-2-one (5,
Fig. 5 and 7) to 2-deuterio-1-octene [7]. The preferred form of the 1,2-disubstituted alkene after protonation of the
lithium intermediate 3 (Fig. 2) is the Z-isomer [7].
The intermediates like 3 (Fig. 2), can be usually treated with other electrophiles like dibromoethane for instance,
to give rise to vinyl bromides, or acetaldehyde to give allyl alcohols or carbon dioxide to give acrylic acids [7] (Fig.
5 and 7). The hydrazone more adequate in these reactions is the 2,4,6-triisopropylbenzenesulphonylhydrazone to
provide the vinyl-lithium, instead of the p-toluensulphonyl [7]. This latter hydrazone suffers lithiation at the ortho
position of the aromatic ring, provoking thus a diminution of the yields in the substituted alkene [7]. This fact is
avoided using the triisopropyl derivative [7,11,12]; see Fig. 5 and 7.

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REVISTA BOLIVIANA DE QUMICA (Rev.Bol.Quim.)


Bolivian Journal of Chemistry
Received 10 11 2015

Vol. 32, No.4, pp. 82-89, Sep./Nov. 2015


32(4) 82-89, Sep./Nov. 2015
Published 11 11 2015

Accepted 10 28 2015
Bravo et Vila
CH3

CH3

NH S
H2N
.. O

.. NH
HN

H+

+ H+

O
CH3

CH3

CH3

NH S
O
+
NH

S
O

CH3

..
..

N-

N
C4H9-Li+

Li+

S
O

N
C4H9-Li+

CH3

CH3

CH3

N- S
.. O

-H+

-H2O

O+H2
CH3

..

N S
O

CH3

NH S
O
H2N+

..

CH3

O
(-)
:S

..
..

O
+

N- Li

N
H

H (-)

CH3

Li+
(-)

..

Li

H
H2O

+ LiOH

Figure 3. Pinacolone transformed into 3,3-dimethyl-1-butene via arylsulphonylhydrazone, as only product; mechanistic
explanation, based in the mechanism exposed in Fig. 2, reviewed by W. Carruthers [7]
CH3

O
NH S
O
H2 N

..

H2+N

NH

NH

p-CH3C6H4O2S

C4H9-Li+

p-CH3C6H4O2S

NH

p-CH3C6H4O2S

N-Li+

NH

O+H2

p-CH3C6H4O2S

Li+ (-)

-H2O

..

H
H
C4H9-Li+

-H+

OH

p-CH3C6H4O2S
H

+H +

HN

O-

H
N
p-CH3C6H4O2S

N-Li+

p-CH3C6H4O2S-Li-

N- Li+

(-)

.. Li+

N
p-CH3C6H4O2S-Li-

Li

p-CH3C6H4O2S-Li-

D2O

D
p-CH3C6H4O2S-Li-

Figure 4. Phenylacetone transformed into 3-phenyl-2-deuterio-propene via arylsulphonylhydrazone as only product;


mechanistic explanation, based in the mechanism exposed in Fig. 2, reviewed by W. Carruthers [7]
CH3

CH3

CH3

O 4

NNHSO2Ar

CO2H

C3H7-iso
C4H9Li

NNHSO2
H3C

C3H7-iso

Li
C6H13

C6H14-TMEDA

C6H13

CO2

C6H13

HO
CH3CHO

C3H7-iso

Br
Br

[Br]

C6H13

Br
C6H13

Figure 5. Conversion of 2-methylcyclohexanone (4) into 2-deuterio-3-methylcyclohexene via p-toluensulphonylhydrazone;


conversion of octan-2-one (5) into 2-deuterio-1-octene via 2,4,6-triisopropylbenzenesulphonylhydrazone; treatment of lithium
intermediate with dibromoethane, acetaldehyde, or carbon dioxide; reviewed by W. Carruthers [7]

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REVISTA BOLIVIANA DE QUMICA (Rev.Bol.Quim.)


Bolivian Journal of Chemistry
Received 10 11 2015

Vol. 32, No.4, pp. 82-89, Sep./Nov. 2015


32(4) 82-89, Sep./Nov. 2015
Published 11 11 2015

Accepted 10 28 2015
Bravo et Vila

Reduction of tosylhydrazones derived from carbonyl compounds into hydrocarbons[7].


This can be achieved by using sodium cyanoborohydride in acid [7]. An alternative to the Wolf-Kishner
deoxygenation is the using of catecholborane [7]. When the hydrazones derivatives are -unsaturated, it is possible
to form alkenes where the double bond has moved to the original carbonyl position [7]. The reducing agent is
usually NaBH(OCOCH3) coming from the mixture: NaBH4 and acetic acid [7,13]. A tentative mechanism has been
proposed where the formation of the diazene intermediate suffers a migration of hydride (15) from N to C [7]. See
Fig. 8, 9 and 10.
p-CH3C6H4O2S

NH

H2N:

p-CH3C6H4O2S

p-CH3C6H4O2S

H2N+

NH

NH

p-CH3C6H4O2S

HN

NH

HN:

O
O-

O+H2 -H2O

OH H+

4
p-CH3C6H4O2S

p-CH3C6H4O2S

H+N

NH

NH

Li+
N-

p-CH3C6H4O2S

C4H9-Li+

-H+

p-CH3C6H4O2S

Li+
p-CH3C6H4O2S-: :N -

Li+
N-

:-

Li+

C4H9-Li+

-N

H
H

(-)
.. Li+

H
Li

D
D2O
LiOD

+
H

Figure 6. Conversion of 2-methylcyclohexanone into 2-deuterio-3-methylcyclohexene via p-toluensulphonylhydrazone, based in


the mechanism exposed in Fig. 2, reviewed by W. Carruthers [7]; mechanistic view
C3H7-iso

O
+

N+H2NHSO2C6H2(i-C3H7)3

NHNHSO2C6H2(i-C3H7)3

O-

NH2NHSO2

OH

H+

C3H7-iso

octan-2-one

C3H7-iso

NNHSO2C6H2(i-C3H7)3
O+H2

NN-SO2C6H2(i-C3H7)3

NNHSO2C6H2(i-C3H7)3

Li+

C4H9-Li+

-H+

Li+
N- SO2C6H2(i-C3H7)3

C4H9-Li+
H2CLi+

Li+
N

NLi+

S-O2C6H2(i-C3H7)3

H2C

Li+
.. (-)

Li

H2C

D2O

H2C

H2C

LiOD

-Li+
H3C

CH3CHO

..(-)

OLi

H 2C
H2C

Br

H 2C
Br

CO2

+ LiCH2CH2Br

Br

H2O
H3C

..(-)
H 2C

H3C

..(-)

OH

LiO

H2C

H 2C

H 2C

HO

H2O

H2C

+LiOH

+LiOH

Figure 7. Conversion of octan-2-one (5) into 2-deuterio-1-octene via 2,4,6-triisopropylbenzenesulphonylhydrazone; treatment


of the lithium intermediate with dibromoethane, acetaldehyde, or carbon dioxide, based in the mechanism exposed in Fig. 2,
reviewed by W. Carruthers [7]; mechanistic view
1

H
NNHTos

N NH

Tos

NaBH4

-TosOH

N2

CH3CO2H

Figure 8. Mechanism for the reduction of tosylhydrazones derived from carbonyl compounds into hydrocarbons; reviewed by
W. Carruthers [7]

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Bolivian Journal of Chemistry
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Vol. 32, No.4, pp. 82-89, Sep./Nov. 2015


32(4) 82-89, Sep./Nov. 2015
Published 11 11 2015

Accepted 10 28 2015
Bravo et Vila

3X
H

BNa+

B-

+3CH3COOH

Na+

AcO

+3CH3COO- + 3H+

OAc

BNa+
AcO

3X
H

+3H2

Figure 9. Reduction of tosylhydrazones derived from carbonyl compounds into hydrocarbons; acetylation of sodium
borohydride to afford sodium boroacetylhydride; mechanistic view
H
..
N N

H
N N

Na+ -

Tos

AcO

+ Na+ S

Na+

Tos

CH3

OAc

AcO

AcO

AcO

OAc

B-

OAc

AcO
AcO

N
H

N
O

AcO

+ Na+ S

CH3

OAc

AcO

Figure 10. Reduction of tosylhydrazones derived from carbonyl compounds into hydrocarbons; action of sodium
boroacetylhydride to afford diazene intermediate followed by 1,5-migration of hydride from nitrogen to carbon, according to
mechanism of Fig. 8, reviewed by W. Carruthers [7]; mechanistic view

Moreover, the use of sodium borodeuteride/acetic acid [NaBD4 + 3CH3COOH NaBD(CH3COO-)3], or on the other
hand the use of carboxyl deuterated acetic acid/sodium borohydride, conducts to the regio-selective introduction of
deuterium (one or two units) [7]. When deuterated acetic acid is employed, the interchange at the N-H position with
deuterium should be faster than the process of reduction (hydride transfer toward carbon) [7]. See Fig. 11, 12 and 13.
NaBD4

NNHTos

CH3CO2H

NaBH4

CH3CO2D

Figure 11. Reduction with sodium borodeuteride in acetic acid or carboxyl deuterated acetic acid giving rise to regioselective
introduction of deuterium. Reviewed by W. Carruthers [7]
H
N N

Na+
-

SO2Ar

H
..
N
N
D

Na+

+ CH3COOH

SO2Ar

O
N

+ Na+ S

CH3

D
D

D
B-

D
D

N
N

Figure 12. Reduction with sodium borodeuteride in acetic acid giving rise to regioselective introduction of deuterium;
mechanistic view

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Bolivian Journal of Chemistry
Received 10 11 2015

Vol. 32, No.4, pp. 82-89, Sep./Nov. 2015


32(4) 82-89, Sep./Nov. 2015
Published 11 11 2015

Accepted 10 28 2015
Bravo et Vila

3X
H

BNa+

B-

+3CH3COOD

Na+

Na+
AcO

3X

Na+
-

SO2Ar

H
..
N N

+CH3COOD

SO2Ar

OAc

B-

N N

AcO

+3CH3COO- + 3H+

O
N

+ Na+ S

Na+

+3HD

CH3

AcO

OAc

AcO
H

AcO
B-

+CH3COOH

AcO
OAc

OAc

AcO

AcO

AcO

+ Na+ S

CH3 +

OAc

+ CH3COOH + N2

AcO

Figure 13. Reduction with sodium boroacetylhydride in carboxyl deuterated acetic acid giving rise to regioselective
introduction of deuterium; mechanistic view
Ketones are also precursors of alkenes by the way of derived enol ethers or enol esters [7]. This is achieved by reductive cleavage
or by coupling with organocuprates [7]. The substrate to be reduced by the using of lithium and amines is the N,N,N,Ntetramethylphosphordiamidates. The cleavage occurs on the C-O bond [7]; with enol derivatives it conducts to the corresponding
alkene with good yields [7,14]. See Fig. 14 and 16.
OC(CH3)3

OC(CH3)3
(1) LiN(iso-C3H7)2
(2) [(CH3)2N2]POCl
(3) Li, NH3, t-C4H9OH

Figure 14. Reductive cleavage of ketones to form alkenes by the way of derived enol ethers . Reviewed by W. Carruthers [7]

The enol can be reduced, it means see its oxygen replaced by an anion, rather by a carbanion (alkyl), instead of a
hydride (a basic hydrogen), by the reaction of the enol diphenylphosphate or the enol trifluoromethanesulphonate
(triflate) with lithium dialkylcuprate [7,15,16]. See Fig. 15. The high stereoselectivity characterizes these reactions
[7]. As an example let us examine the transformation of (Z)-5-trifluoromethanesulphonyloxy-5-decene into (E)-5methyl-5-decene by using dimethyl cuprate [7]. See Fig. 15
TfO

C4H9

C 4 H9

(CH3)2CuLi

H3 C
C 4 H9

C4H9
H

(Tf = CF3SO2)

CF3 O
S
O
O

CF3 O
S
O
O-Li+ H3C

Li++ 2CH3- + Cu+

+ CH3Cu

Figure 15. Replacement or reduction of the enols oxygen atom by a n alkyl group instead of H. using triflate with lithium
dialkylcuprate. Reviewed by W. Carruthers [7]. Mechanistic view

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.. i-pr
Li+ :-N
i-pr

Accepted 10 28 2015
Bravo et Vila
O

H
.. i-pr
+
HN
+ Li :C
i-pr

H
O

Me2N

Cl

P+

+ + Li Cl

Me2N

Me2N

Li+

Me2N

Cl

Me2N

Me2N

Li+ O

Vol. 32, No.4, pp. 82-89, Sep./Nov. 2015


32(4) 82-89, Sep./Nov. 2015
Published 11 11 2015

H
C

O
Me2N

P NMe2
O

Li+ + 1e-

Li
NH3 + HOC4H9
NH4+

NH4+ + -OC4H9
NH3 + H+

Li+ + -OC4H9

LiOC4H9

H+ + 1e-

H
Li+ + 1e-

Li
H + 1e-

H-

NH3 + HOC4H9

NH4+ + -OC4H9

NH4+ + -OC4H9

NH4OC4H9

H- + Li+
2Li + 2NH3 + 2HOC4H9

LiH
NH3 + NH4OC4H9 + LiH + LiOC4H9

H
C

O
Me2N

LiO
+

Me2N

P NMe2
O

H
NMe2

Li+H-

Figure 16. Reductive cleavage of ketones to form alkenes by the way of derived enol ethers. Mechanistic views.

In Fig. 16 the basic nitrogen temporally stabilized by the cation Li+, withdraws the proton in of carbonyl in the
ketone. This is due to its acidic character. A carbanion appears in the place of the -hydrogen. Because the oxygen
supports better than the carbon atom a negative charge in excess, an inductive current generates the migration of the
two electrons over the carbon atom for establishing a new C2=C3 double bond and placing the negative charge over
the oxygen of the ketone now transformed into an enol oxygen. Oxygen is now temporally stabilized by Li+. This
lithium enol interacts now with chloride from phosphorus derivative {[(CH3)2N]2POCl} thus generating the
corresponding cation with the positive charge reposing on the phosphorus. What is next is the oxidation of two
equiv. of Lithium metallic plus the using of two equiv. of ammonia as well as two equiv. of n-butanol to give one
ammonia, a n-butoxylammonium, a lithium-n-butoxyl and a lithium hydride. This hydride is responsible of the
reduction of the enol into an alkene function.
ACKNOWLEDGEMENTS
The authors express their gratitude to Prof. Eduardo Palenque from the Department of Physics, Universidad Mayor
de San Andrs, for his bibliographic support.
REFERENCES

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Accepted 10 28 2015
Bravo et Vila

Vol. 32, No.4, pp. 82-89, Sep./Nov. 2015


32(4) 82-89, Sep./Nov. 2015
Published 11 11 2015

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