Stereospecific Synthesis of Alkenes From 1,2-Diols Mechanistic Views The Organic Chemistry Notebook Series, A Didactical Approach, #8

REVISTA BOLIVIANA DE QUMICA (Rev.Bol.Quim.
)
Bolivian Journal of Chemistry
Received 12 14 2015
Accepted 12 23 2015
Bravo et Vila
Vol. 32, No.5, pp. 121-125, Nov./Dic. 2015

32(5) 121-125, Nov./Dec. 2015
Published 12 30 2015
.
STEREOSPECIFIC SYNTHESIS OF ALKENES FROM 1,2-DIOLS;

MECHANISTIC VIEWS; THE ORGANIC CHEMISTRY NOTEBOOK
SERIES, A DIDACTICAL APPROACH, N 8
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, Alkenes, 1,2-diols, Stereospecific synthesis, Mechanisms of

Reactions, W. Carruthers.
ABSTRACT
This is the eighth chapter in the series: 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 discuss, from a mechanistic stand point, some methods for the stereospecific synthesis of
alkenes from 1,2-diols. One of the best ones utilizes as precursors, the cyclic thionocarbonates obtained from the diol
with thiophosgene. We describe by mechanisms, the use of 1,3-dimethyl-2-phenyl-1,3,2-diazophospholidine as an
alternative for the decomposition of thionocarbonates into alkenes. We discuss by mechanisms, a general and
unambiguous method for the interconversion of Z- and E-alkenes. Thus, the conversion of the (Z)-cyclooctene into
the E isomer is detailed here. The mechanism of the conversion of meso-1,4-diphenylbutan-2,3-diol into (Z)-1,4diphenyl-2-butene is here described. 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
estereoespecfica de alquenos a partir de 1,2-dioles; vistas mecanicsticas; de la serie: El cuaderno de notas de qumica orgnica, un enfoque
didctico, N8.
*Corresponding author: joseabravo@outlook.com

INTRODUCTION
During master classes of organic chemistry we noticed 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 about 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 stereospecific synthesis of alkenes from 1,2-diols, is the eighth
study in: The Organic Chemistry Notebook Series, a Didactical Approach [1-7].
REACTIONS AND THEIR MECHANISTIC PROPOSALS, DISCUSSION
The synthesis, regiospecific and stereospecific of double bonds, is feasible from 1,2-diols [8]. All procedures include
the formation of an intermediate of the type 1 (Fig. 1), which decomposes into products [8]. One of the best of the
various methods available uses the cyclic thionocarbonates 3, (Fig. 1) [8]. These are obtained from reaction of the
diol with thiophosgene, Fig. 1 [8]. The fragmentation started with the thionocarbonates transformed into alkenes by
heating with triethylphosphate; more recently, the conversion is done only at 25-40 C by using thionocarbonate with
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REVISTA BOLIVIANA DE QUMICA (Rev.Bol.Quim.)

Received 12 14 2015
Vol. 32, No.5, pp. 121-125, Nov./Dic. 2015

32(5) 121-125, Nov./Dec. 2015
Accepted 12 23 2015
Bravo et Vila
1,3-dimethy-2-phenyl-1,3,2-diazophospholidine [8,9]. It is believed a concerted process or a process that includes an

intermediate carbene (2) [8].
R2
R2
O
R4
O
C:
R4
2
CH3
N
Cl
C
OH
C6H5
C6H5
C6H5
CH2Cl2, 0C
C6H5
OH
CH3
Cl
C6H5
CH3
C S
C6H5
C6H5
CH3
CHCl3, 40C
O
CH3
3
Figure 1. Synthesis, regiospecific and stereospecific of double bonds; feasible from 1,2-diols; reviewed by W. Carruthers [8]
The mechanistic approach to the reactions appearing in Fig. 1, are exposed in Fig. 2.
Ph
Ph
..
OH
Ph H
Ph
H
O+
Ph H
Ph H
+ HCl
OH Cl
H3C
H3C
OH
C
Cl
Cl
H3C
Cl
+ HCl
H3C
Cl
Ph H
O+
H3C
OH
..
C
S
Cl
S-
Ph
Ph H
O
Ph H
S+ HCl
The concerted process mechanism step by step

Me
Me
Me
N
N
P
Ph H
O:
H3C
Ph
:O :
..
O
..
C
Me
..
O
..
Ph
Me
Me
N
Me N:
N+
Ph
Ph
P Ph
: O:
..
O
..
C
H
CH2 + MeN NMe +
O C
Ph
..
O
..
O
.. :
C
S
H3C
S
Ph
C
:O :
Ph H
..
+O
..
H3C
C
Ph H
..
O
..
Ph
Ph
Me
Me
N
Ph
Ph
H3C
Me
Me
N
H2C
O
.. :
Me
S + Ph
Ph
Ph
Me
P O +
The concerted process mechanism in one step

Me
Me
Me
N
Me
N
N
P-
Ph
Ph
Ph
Ph H
H3C
O:
..
O
..
C
S
one step (concerted)
Ph
..
O
..
H
P Ph
: O:
Me
H2C
CH2 + MeN NMe
Me
H3C
Figure 2. Synthesis, regiospecific and stereospecific of double bonds; feasible from 1,2-diols; mechanistic proposal
Comments
In Figure 2, a nucleophilic attack from the oxygen of the diol over the carbon of the analogue-of-carbonyl C=S, is
shown in the first step. The protonated ether formed eliminates a HCl to afford an analogue of a thioester, the S=C-O
(with the bond 'pi' shared between O and S [S-C=OS=C-O]). The carbon of C=S (analogue-of-carbonyl) suffers a
new nucleophilic attack, this time from the other hydroxylic oxygen to replace another chloride that correlates with
122

Received 12 14 2015
Vol. 32, No.5, pp. 121-125, Nov./Dic. 2015

32(5) 121-125, Nov./Dec. 2015
Accepted 12 23 2015
Bravo et Vila
the liberated H from the just formed ether linkage (second HCl). Now, both oxygens are activated by the
thionocarbonate toward elimination. However the process takes place only due to the catalysis-type action of the 1,3dimethy-2-phenyl-1,3,2-diazophospholidine. The term concerted mechanism implies an only step when all
excision-formation of bonds occur simultaneously. It is also implied the absence of ions, however with didactical
purposes we explain the concerted mechanism (an only step) in three derived steps that include precisely ions.
Besides the alkene, the residue is an eight-membered polyheterocycle. Also, we propose a disintegration of this cycle
that occurs in one concerted step, in three didactical steps. The resulting four-membered diazocycle, disintegrate in a
concerted way. The final products are: the alkene pursued, ethylene, azomethane [10], carbonyl sulfide [11], and
PhP=O.
Given the mild conditions, the reaction can be used in the synthesis of complex molecules and sensitive due to
the presence of many functional groups [8]. As an example, the 3,5-acetonide of the complex macrolide named as
erythronolide A, can be transformed into the 11,12-deoxy derivative; hence, the diol 4 gives 5, with a yield of 75 %
[8]. The reactions proceed by keeping stereospecificity following a syn elimination route [8]. This is an excellent
method to produce cycloalkenes suffering strain due to 1,2-substituents mutually hindered [8]; see Fig. 3. This
method and the trans perhydroxylation [12] constitute the virtuous cycle for the isomerization between Z- and Ealkenes [8]. Figure 4 shows the corresponding mechanisms.
OCH3
OCH3
OH
O
H3C
OH
H3C
OCH2C6H5
OCH2C6H5
Figure 3. Synthesis of 11,12-deoxyerythronolide A; reviewed by W. Carruthers [8]
OCH3
OH
O
H3C
OH
OH
OCH2C6H5
OH
OH
..
+ HCl
O
Cl
+ OH
Cl
OH
OH
OH
..
Cl
Cl
Cl
S
S-
S
CH3
C6H5
+ OH
Cl
O
P
N
Me
N
Me
N
S
N
S
Me
Me
Ph
N
N
O Ph
O
P
N
Me
N
Me
O+
O
Ph
S
C
O Ph
O
P +
N
Me :N
Me
Ph
S
C
S
S
Ph
O
O
+ HCl
SS
CH3
Me
Me
S=C=O + O=P-Ph + MeN=NMe + CH2=CH2 +
Me
Me
OCH3
O
H3C
OCH2C6H5
5
Figure 4. Synthesis of 11,12-deoxyerythronolide A; mechanistic views
Comments
The same remarks done for Fig. 2 are applicable for Fig. 4.
Other examples are the conversion of meso-1,4-diphenylbutan-2,3-diol into (Z)-1,4-diphenyl-2-butene [8], and
the synthesis of its E-isomer starting from the dl-1,4-diphenylbutan-2,3-diol [8]. The mechanistic development of
these transformations is pictured in Fig. 5 and 6 respectively.
123

Received 12 14 2015
Ph
Accepted 12 23 2015
Bravo et Vila
OH
H OH H OH
Ph
180o H
Vol. 32, No.5, pp. 121-125, Nov./Dic. 2015

32(5) 121-125, Nov./Dec. 2015
OH
OH
OH
OH
Ph
180o
HO
H OH H OH
180o
OH
..
OH H
Ph
rotamer A
rotamer C
rotamer B
+ HCl
Cl
OH
OH H Cl
H
OH
..
S-
H
+ HCl
O
+O
Cl
+O
N
Me
O Me Me
O
H
O Me Me
:N
P
O
N
N
Me
Me
S
(Z)-1,4-diphenyl-2-butene Me
S
Me
N
S=C=O
O=P-Ph
Me
+N
SCO + OPPh + MeNNMe + H2CCH2
N
Me
Ph
Ph
Figure 5. Synthesis of (Z)-1,4-diphenyl-2-butene from meso-1,4-diphenylbutan-2,3-diol; mechanistic view

S
Ph
H
HO
H OH OH
H
Ph1
OH
H
OH
HO
180o
Ph
Cl
C
H OH OH
H
OH
HO
Cl
HO
H
1
CL
Cl
..
180o
S
Cl
Cl
180o
+ OH
2
H
1
Ph2
dl-1,4-diphenylbutan-2,3-diol
Cl
HO
S
CL
HO
..
HO
H
1
Cl
S-
S
+ HCl
..
+ OH
H
S
Cl
Cl
O
HO +
H
+ HCl
CH3
Me
N
O
1
C6H5
Ph
N
P-
Ph
Me
CH3
Me
P-
Me
Me
N
S
O
H
Me
O
H
O+
OH
Ph
Me
N
-N
Ph
C
S
(E)-1,4-diphenyl-2-butene
Me
+N
C
S
Me
N
Ph
Me
+ HCl
H
P
H O
Ph
HP
O H
+ HCl
Ph
HP
Cl
Cl
meso-1,4-diphenylbutan-2,3-diol
Me
N
MeNNMe + SCO + PhPO + CH2CH2
Figure 6. Synthesis of (E)-1,4-diphenyl-2-butene from dl-1,4-diphenylbutan-2,3-diol; mechanistic view
Figure 7 represents the isomerization ZE of (Z)-cyclooctene as reviewed by W. Carruthers [8].

trans
OH
OH
C
hydroxylation
(CH3O)3P
100 - 130 oC
(75%; 99% E)
Figure 7. Conversion of (Z)-cyclooctene into its E-isomer; reviewed by W. Carruthers [8]

124

Received 12 14 2015
Accepted 12 23 2015
Bravo et Vila
Vol. 32, No.5, pp. 121-125, Nov./Dic. 2015

32(5) 121-125, Nov./Dec. 2015
.
Figure 8 shows mechanistically how (Z)-cyclooctene can be converted in its E-isomer [8], following a similar
protocol to the one used previously in this discussion. Alternatively, another derivative of 1,2-diol, the benzylidene,
can be treated with butyl-lithium [8]. This method is however of limited application, given the high susceptibility of
many functional groups toward the butyl lithium [8]. The method is suitable with lightly substituted alkenes only
[8,13]. Other methods with stereospecificity include acetals derived from the diol with ethyl-orthoformate [8,14], or
N,N-dimethylformamide dimethyl acetal [8,15].
S
Cl
Cl
OH
trans
hydroxylation
(Z)-cyclooctene
S
H
:OH
O
Cl
Cl
..
OH
H
H
OH
OH
Cl
+ OH
+ HCl
H
OH
H
OH
S
O
Cl
Cl
OH
+
S
O
H
H
(CH3O)3P
100 130 oC
H
O+
+ HCl
P- O
O
+
S-
O-
+ P(OCH3)3
(E)-cyclooctene
O
C
S
(75%; 99% E)
Figure 8. Conversion of (Z)-cyclooctene into its E-isomer; mechanistic view
ACKNOWLEDGEMENT
The authors express their gratitude to Prof. Eduardo Palenque from the Department of Physics, Universidad Mayor
de San Andrs, for his bibliographic support.
REFERENCES
1.
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Bravo, J. 2005, Rev. Bol. Quim., 23, 1.

Bravo, J.A., Mollinedo, P., Pearrieta, J.M., Vila, J.L. 2013, Rev. Bol. Quim., 30, 24.
Bravo, J.A., Vila, J.L. 2014, Rev. Bol. Quim., 31, 61.
Vila, J.L., Bravo, J.A. 2015, Rev. Bol. Quim., 32, 37.
Carruthers, W. Some Modern Methods of Organic Synthesis, Cambridge University Press, 3rd ed., 1987, Worcester, U.K., pp.
162-165.
Corey, E.J., Hopkins, P.B. 1982, Tetrahedron Lett., 23, 1979.
Rebbert, R.E. , Ausloos, P. 1962, J. Phys. Chem., 66, 2253.
Protoschill-Krebs, G., Wilhelm, C., Kesselmeier, J. 1996. Atmospheric Environment, 30, 3151.
Carruthers, W. Some Modern Methods of Organic Synthesis, Cambridge University Press, 3rd ed., 1987, Worcester, U.K., pp.
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