Revista Boliviana de Química

ISSN: 0250-5460
revbolquim@outlook.com
Universidad Mayor de San Andrés
Bolivia

Bravo, José A.; Vila, José L.

MECHANISTIC VIEWS OF STEREOSELECTIVE SYNTHESIS OF TRI-AND TETRA-
SUBSTITUTED ALKENES, PART II; THE ORGANIC CHEMISTRY NOTEBOOK SERIES,
A DIDACTICAL APPROACH, Nº 4
Revista Boliviana de Química, vol. 32, núm. 1, enero-junio, 2015, pp. 15-23
Universidad Mayor de San Andrés
La Paz, Bolivia

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REVISTA BOLIVIANA DE QUÍMICA Vol. 32, No.1, pp. 15-23, Ene./Abr. 2015
Bolivian Journal of Chemistry 31(2) 15-23, Jan./Apr. 2015
Received 03 23 2015 Accepted 04 15 2015 Published 04 30 2015
Bravo et Vila .

MECHANISTIC VIEWS OF STEREOSELECTIVE SYNTHESIS OF TRI-

AND TETRA-SUBSTITUTED ALKENES, PART II; THE ORGANIC
CHEMISTRY NOTEBOOK SERIES, A DIDACTICAL APPROACH, Nº 4
José A. Bravo*, José L. Vila
Department of Chemistry, Laboratorio de Síntesis y Hemisíntesis, Instituto de Investigaciones en Productos
Naturales IIPN, Universidad Mayor de San Andrés UMSA, P.O. Box 303, Calle Andrés Bello s/n, Ciudad
Universitaria Cota Cota, Tel. 59122792238, La Paz, Bolivia

Keywords: Organic Chemistry, Stereoselective synthesis, Alkenes, Addition reaction,

Mechanisms of Reactions.

ABSTRACT

This is the complementing part of the previously published: “Mechanistic views of stereoselective synthesis of tri-
and tetra-substituted alkenes, part I; The Organic Chemistry Notebook Series, a Didactical Approach, Nº 3”. As
underlined in three previous papers the presentation of synthesis works in a verbal and graphical succinct manner,
needs a didactical approach. Isomerically pure tri- and tetra-substituted alkenes are difficult to obtain as shown in
several publications. We used a series of reactions to synthesize tri- and tetra-substituted alkenes as reviewed by W.
Carruthers, and we have proposed didactical and mechanistic views for the reviewed reactions. These two latest
approaches are included in the synthetic methods reviewed by W. Carruthers with respect to the “Formation of
carbon-carbon double bonds”. Spanish title: Vistas mecanísticas de síntesis estereoselectivas de alquenos tri y tetrasubstituidos, Parte II,
Serie: El cuaderno de notas de química orgánica, un enfoque didáctico, Nº4.

*Corresponding author: jabravo@umsa.bo

ANALYSIS AND MECHANISTIC PROPOSALS

As academics we are concerned with the didactical importance of covering the needs of debutant students in organic
synthesis. This is the fourth study in: “The Organic Chemistry Notebook Series, a Didactical Approach” [1-3]. The
present article is the completion of the analytical and didactical approach to stereoselective synthesis of tri- and tetra-
substituted alkenes as reviewed by W. Carruthers [4], and illustrated mechanistically by J. Bravo and J. Vila [3]. Tri-
and tetra-substituted alkenes are difficult to obtain. Authors [4] mentioned other methods signaled as useful for the
stereospecific synthesis of alkenes starting with alkynes. The procedure starts with alkenylalanes and alkenylboranes.
The first are obtained by hydroalumination of alkynes with e.g. diisobutylaluminium hydride. The addition is cis
type, giving rise to Z-alkenylalanes. The Z-alkenylalanes react with halogens with retention of configuration to afford
alkenyl halides. The halogen atoms can be replaced by alkyl groups by means of reacting with an organocopper
reagent. Iodination of the alane obtained from reaction of 1-hexyne with diisobutylaluminium hydride makes
possible the (E)-1-iodo-1-hexene. 3-hexyne gives (E)-3-iodo-3-hexene [4]. See Figure 1 for the reactions reviewed
by W. Carruthers [4].

(iso-C4H9 )2AlH H Al(iso C4H9)2 (1) I , THF, -50oC H I

C4H9 C C H C C
2
C C
+
C7H16 C4H9 (2) H3O C4H9
H H
(74%)

(iso-C4H9 )2AlH C2H5 C2H5 o C2H5 C2H5

C2H5 C C C2H5 (1) I2, THF, -50 C
C C C C
+
C7H16 H Al(iso C4H9)2 (2) H3O H I
(72%)
Figure 1. Obtention of alkenyl halides via alkenylalanes [(E)-1-iodo-1-hexene and (E)-3-iodo-3-hexene; reviewed by W.
Carruthers [4]

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REVISTA BOLIVIANA DE QUÍMICA Vol. 32, No.1, pp. 15-23, Ene./Abr. 2015
Bolivian Journal of Chemistry 31(2) 15-23, Jan./Apr. 2015
Received 03 23 2015 Accepted 04 15 2015 Published 04 30 2015
Bravo et Vila .

Figure 2 shows the mechanistic proposal for these reactions.

(iso-C4H9 )2Al H (iso-C4H9 )2Al+
..
(iso-C4H9 )2Al+ + O
..
-
+ I + I
+

H
H H
C C H C C:- (iso-But)2Al C:-
H

H H
1-hexyne

optionally:
I H O+ I+
.. (iso-But)2Al- 1st 2nd H .. ..
O+ + I
- O+ + I
- O+
+ +
Al(i-But)2 Al(i-But)2 Al-(i-But)2
H
H
I
(E)-1-iodo-1-hexene

.. + I2
O
..
(iso-C4H9 )2Al H +
(iso-C4H9 )2Al

O+ I+
H 2nd
(iso-But)2Al (iso-But)2Al- 1st
C C C C:-

H H
3-hexyne

I ..
.. O+
O+ + I
-
+ Al-(i-But)2
Al(i-But)2
H
I
(E)-3-iodo-3-hexene

Figure 2. Synthesis of (E)-1-iodo-1-hexene and (E)-3-iodo-3-hexene, mechanistic views

Alternatively, Z- and E-1-halogenoalkenes can be obtained from terminal acetylenes by means of the use of E-
alkenylboronic acids which can be synthesized by reaction of terminal acetylenes with catecholborane and
subsequent hydrolysis [4]. Boronic acids react with sodium hydroxide to replace the boronic acid group by iodine to
afford E-1-iodoalkene; retention of configuration occurs [4]. If the reaction is carried out with bromine and base, the
substitution result implies inversion; Z-1-bromoalkene is obtained [4]. In both reactions, the stereoselectivity is high;
for example, 1-octyne gave (Z)-1-bromo-1-octene (85% yield, 99% stereoselectivity), and 1-hexyne gave (E)-1-iodo-
1-hexene [4]. Figure 3 and 4 show the global reactions and the mechanistic approach, respectively.
O
1) BH
C4H9 H (1) I2
C4H9 H
O
C4H9 C C H C C C C
(2) NaOH
2) H3O+ H B OH H I
HO (89%; more than 99% E)
O
1) BH
C6H13 H (1) Br2, CH2Cl2
C6H13 Br
O
C6H13 C C H C C C C
(2) NaOCH3
2) H3O+ H B H H
CH3OH
(85%; 99% Z)
Br H Br Br
R H R R R Br
Br2 rotate 120o CH3O-
C C C C B C C H C C
H NaOCH3 H H H
B Br B H

Figure 3. Obtention of (E)-1-halogenoalkenes from terminal acetylenes via E-alkenylboronic acids. Inversion of configuration
during bromination. Reviewed by W. Carruthers [4]

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REVISTA BOLIVIANA DE QUÍMICA Vol. 32, No.1, pp. 15-23, Ene./Abr. 2015
Bolivian Journal of Chemistry 31(2) 15-23, Jan./Apr. 2015
Received 03 23 2015 Accepted 04 15 2015 Published 04 30 2015
Bravo et Vila .

Inversion of configuration in brominating is explained by the trans-addition of Br2 to the double bond and
ulterior trans-elimination of boron and bromine due to NaOCH3 ([4], Figure 3).

O O H
H B H H
+
C C _ O C C H3 O+
B O B O
C C H
O
H
1-hexyne
H H H
H H H
C C + H H2O C C H H2O C C H
B O B O B O
O O O+H 2 O+ OH
H

H2O

H H _ H
H H + H
C C H C C _ OH Na C C:
B O
Na+OH- B Na+ I- + I+
OH + H+ HO OH
O
H
OH

H OH O O
H H B C6H13 + H
C C OH C C _ O
I + B O
I- + Na + B(OH)3 + C6H13 C C H
1-octyne
H

Br+ Br+

H H C6H13 Br H
C6H13 C6H13
C C + -
C C C C-:
B O Br Br B O B O
H H H
O O O

Br-

C6H13 Br H C6H13 Br Br O
Br H Br Br
C C C6H13 C6H13 C C B
Br rotate 120 o Na+O-CH3
C C B C C H
H H H O
H Br H B
B O
O

Na+
Na+
C6H13 Br _ Br O C6H13 Br Br C6H13 Br
B
.. _ O O
C C C C C C
H + CH3O B H + NaBr + BOCH3
H H O H H O
OCH3 O

Figure 4. Obtention of (E)-1-halogenoalkenes from terminal acetylenes via E-alkenylboronic acids. Inversion of configuration
during bromination, mechanistic view

On other topics, the reviewer mentions αβ-unsaturated carboxylic acids obtained from aluminates that at their
turn were afforded by alkenylalanes after reaction with methyl-lithium. In the same manner, paraformaldehyde and
other similar compounds give rise to allylic alcohols [4,5]. The difference between this reaction and the one
previously exposed regarding hydroalumination of disubstituted acetylenes with lithium
hydridodiisobutylmethylaluminate obtained from diisobutylalumimium hydride and methyl-lithium, is the trans
addition to the alkyne multiple bond [4,5]. Carbonation gives αβ-unsaturated carboxylic acids. The reaction with
paraformaldehyde/acetaldehyde gives allylic alcohols; iodine, alkenyl iodides. All these derivatives are isomeric with
compounds obtained using diisobutylalumimium hydride discussed previously [4,6]. Both isomers cis and trans α-
methylcrotonic acids were obtained from 2-butyne [4,6]. Figure 5 shows the reaction sequences; Figure 6 the
applicable theoretical mechanistic proposals. ‘In all these reactions the isobutyl groups of the hydroaluminating agent

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REVISTA BOLIVIANA DE QUÍMICA Vol. 32, No.1, pp. 15-23, Ene./Abr. 2015
Bolivian Journal of Chemistry 31(2) 15-23, Jan./Apr. 2015
Received 03 23 2015 Accepted 04 15 2015 Published 04 30 2015
Bravo et Vila .

are converted into isobutane in the hydrolysis step, and do not interfere with the isolation of the products’ (W.
Carruthers [4]). See Figure 6.

(iso-C4H9 )2AlH CH3 CH3 CH3 CH3 CH3 CH3

CH3Li, ether, -30 C
o CO2, H3O+
CH3 C C CH3 C C C C
C C Li+
H - H
2-butyne Al(iso-C4H9)2 H Al(iso-C4H9)2 CO2H
(76%)
CH3
(1) paraformaldehyde
CO2, H3O+ H CH3
(2) H3O+
C C
H CH3 CH3 CO2H
C C
(72%)
CH3 CH2OH
(68%)
Figure 5. Obtaining of αβ-unsaturated carboxylic acids and allylic alcohol from aluminates; reviewed by W. Carruthers [4]

(iso-C4H9)2Al+

CH3 CH3 CH3 CH3 Li+ CH3- CH3 CH3

C C C C:- C C C C
H H Al(iso-C4H9)2 H Al(iso-C4H9)2
(iso-C4H9)2Al H
2-butyne
Li+ Li+

CH3 CH3 CH3 _ CH3 CH3 CH3 H3O+

Al(iso-C4H9)2
C C _ C C: + C C
Al(iso-C4H9)2 CH3 _ O
H H H
O O
C
CH3 O Li+
(iso-C4H9 )2Al +
H (iso-C4H9)2Al
CH3 CH3
C C
O H CH3 H CH3 Li+ CH3-
H C C
HO C C:- C C
CH3 CH3 Al(iso-C4H9)2
cis-crotonic acid + LiOH + Al(iso-C4H9)2 +H+
CH3 2-butyne 2-butyne
Li+ Li+

H CH3 H _ CH3 H CH3 H CH3

C C_ H3O+
C C: C C C C
CH3 Al(iso-C4H9)2 O O
CH3 O O- CH3
CH3 HO
Al(iso-C4H9)2 C
CH3 O trans-crotonic acid + LiOH + Al(iso-C4H9)2 +H+
CH3 Li+
CH3
(iso-C4H9 )2Al H (iso-C4H9 )2Al+
Li+

H CH3 H CH3 Li+ CH3- H CH3

C C C C_
C C:- C C
CH3 Al(iso-C4H9)2 CH3 Al(iso-C4H9)2
CH3
2-butyne
CH3
Li+

H CH3 H CH3 H CH3

_ H3O+
C C: C C O- Li+ C C OH Al(iso-C4H9)2
CH3 + + LiOH + H+
CH3 H CH3 H CH3
H H
Al(iso-C4H9)2
CH3
Solvolysis
HO Osolvolysis HO O H H n-1
CH2 H CH2 H H O CH2++ -O CH2OCH2 O O CH2 +
HO
CH2OCH2
O n-1 O=CH2
n n n-1 n-1
paraformaldehyde formaldehyde paraformaldehyde formaldehyde

O+H2 O+H2 OH OH
- - H2O
C4H9 Al C4H9 + H2O C4H9 Al C4H9 C4H9 Al + C4H9 C4H9 Al + C4H10 C4H9 Al- O+H2
CH3 CH3 CH3 CH3 isobutane CH3
OH OH
Al O+H2 - Al OH
+ C 4H 9 + C4H10
CH3 CH3 isobutane

Figure 6. Obtaining of αβ-unsaturated carboxylic acids and allylic alcohol from aluminates; mechanistic views

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REVISTA BOLIVIANA DE QUÍMICA Vol. 32, No.1, pp. 15-23, Ene./Abr. 2015
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Received 03 23 2015 Accepted 04 15 2015 Published 04 30 2015
Bravo et Vila .

In contrast with alkenylalanes, alkenylboranes (obtainable from hydroboration of alkynes) exhibit a different
comportment. Under iodination, no iodide is produced, instead, the stereospecific transfer of one alkyl group from
boron to its vicinal carbon occurs. This provides an alternative stereospecific synthesis of substituted alkenes [4]. In
this way, iodine and sodium hydroxide added to the alkenylborane obtained after hydroboration of 1-hexyne with
dicyclohexylborane, conducts to (Z)-1-cyclohexyl-1-hexene (75% yield). See Figure 7 for the reaction reviewed by
W. Carruthers [4]. Figure 8 shows the corresponding mechanistic view.
C6H11
C6H11
I- H C6H11 H B I
H
H C4H9 H
(C6H11)2BH H B(C6H11)2 B C6H11 C4H9 C C I C C C C
C4H9 C C H C C
I2, NaOH
C C B
H C6H11
= I
H
C6H11 C4H9 C6H11
C4H9 I
1-hexyne C4H9 H H
I+ (75% Z)

Figure 7. Synthesis of (Z)-1-cyclohexyl-1-hexene employing 1-hexyne as starting material and applying alkenylborane and
subsequent addition of iodine; reviewed by W. Carruthers [4]
H11C6
H
B C6H11

H
B- H B + - - H B
C4H9 C C+ C + Na + I + OH
C H C C C C+
1-hexyne C4H9 H C4H9 H C4H9 H
- +
I : I.. : : ..I :
I
I H H
H B H B- B
C C C C
H
C4H9
C C
B
I
= C4H9
C C
H =
C4H9 H C4H9 I I
H

: ..I + : ..I +

I
H
C4H9 B H H
C C I
C C
H +B
+
+ I- = BI2C6H11
I
C4H9
(75% Z)

Figure 8. Synthesis of (Z)-1-cyclohexyl-1-hexene employing 1-hexyne as starting material and applying alkenylborane and
subsequent addition of iodine; mechanistic views

Similarly, 3-hexyne is transformed in (Z)-3-cyclohexyl-3-hexene [4]; Figure 9 shows the corresponding

mechanism. The “anti” elimination of boron and the iodine atom, reassures the stereoselectivity of the observed
alkenic product in the alkene-forming step [4].

H11C6
H
B C6H11

H
B- H B + - H B
Et C + + Na + I + OH-
C Et C C C C C C+
C2H5
3-hexyne C2H5 C2H5 C2H5 C2H5 C2H5
+
: I.. : : ..I :
-
I

I I
H H
H B H B- B
C C C C
C2H5
C2H5
C C
B
I
= C2H5
C C C2H5
=
C2H5 C2H5 C2H5 I I
C2H5

: ..I + : ..I +

Figure 9. Synthesis of (Z)-3-cyclohexyl-3-hexene employing 3-hexyne as starting material and applying alkenylborane and
subsequent addition of iodine; mechanistic views.

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REVISTA BOLIVIANA DE QUÍMICA Vol. 32, No.1, pp. 15-23, Ene./Abr. 2015
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Received 03 23 2015 Accepted 04 15 2015 Published 04 30 2015
: .. : .. Bravo et Vila .

I
H
C2H5 B H C2H5
C C I
C C + -
C2H5 +B + I = BI2C6H11
I
C2H5

(85% Z) (Z)-3-cyclohexyl-3-hexene

Figure 9. Synthesis of (Z)-3-cyclohexyl-3-hexene employing 3-hexyne as starting material and applying alkenylborane and
subsequent addition of iodine; mechanistic view (Cont.)

Dialkylvinylboranes can be synthesized from dialkylhaloboranes and an internal alkyne in the presence of
lithium aluminium hydride. These can react with iodine in the presence of methoxide to produce trisubstituted
alkenes, stereoselectively. The two substituents of the alkyne are trans to each other [4]. (Z)-3-methyl-3-pentene was
obtained from 2-butyne as Figure 10 shows [4]. The mechanism includes the iodine complex already exposed in
Figures 7 to 9; see Figure 11.

(C2H5 )2BBr (C2H5)2B H CH3 H

CH3 C I2, NaOH
C CH3 C C C C
1/4 LiAlH4, THF CH3 CH3OH, -78º C C2H5
2-butyne CH3 CH3
(74%)
Figure 10. Synthesis of (Z)-3-methyl-2-pentene, a tri-substituted alkene with the two original substituents in alkyne located in
trans to each other; reviewed by W. Carruthers [4]
Li+ H5C2
H3Al- H Br
B C2H5
AlH3 Li+
Li+ H C2H5
Br C2H5
C C :C- C B- H C2H5 B H
CH3 CH3 C C C C
C2H5
CH3 CH3 CH3 CH3
2-butyne
+ AlH3 + LiBr +
I- : I.. :

C2H5 C2H5 H
C2H5 C2H5
C2H5 B H C2H5 B H + - I B- C H H C2H5 CH3
C+ C C C
+ Na OH 2 5
C C I
B C C =
CH3 CH3 CH3 CH3
CH3 CH3 CH3 : ..I :

+I +I
: ..I : .. : .. :

Et I Et
I B H I B- H
CH3 H
CH3 CH3 C C
CH3 C C CH3 C C+ + I2BEt
C2H5 CH3
C2H5 C2H5
: ..I :
(Z)-3-methyl-2-pentene

Figure 11. Synthesis of (Z)-3-methyl-2-pentene, a tri-substituted alkene with the two original substituents in alkyne located in
trans to each other; mechanistic views

Trisubstituted alkenes are also obtained from terminal alkynes by way of the corresponding 1-alkenyl iodides.
Iodide is treated by butyl-lithium, trialkylborane and iodine. The trisubstituted alkene possesses the iodine of the
alkenyl iodide replaced by an alkyl group coming from the borane with retention of configuration. ‘The
stereochemistry of the product requires syn elimination of R2BI’ [4,7,8]. Figures 12 and 13 explain this synthesis.

C2H5MgBr C6H13 H C6H13 H (1) C H Li

C6H13 C C H C C I2 4 9
C C o
CuBr.(CH3)2S C 2 H5 (2) (C2H5)B, -78 C
2-butyne Cu(CH3)2S.MgBr2 C2H5
I
Figure 12. Trisubstituted alkene synthesis by iodination and subsequent treatment with butyl-lithium, trialkylborane and iodine;
reviewed by W. Carruthers [4]

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REVISTA BOLIVIANA DE QUÍMICA Vol. 32, No.1, pp. 15-23, Ene./Abr. 2015
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Received 03 23 2015 Accepted 04 15 2015 Published 04 30 2015
Bravo et Vila .

C6H13 H I2 C6H13 H
C C C C
Li+
C2H5 B-(C2H5)3 C2H5 C2H5
(75%; 95% stereochemically pure)

Figure 12. Trisubstituted alkene synthesis by iodination and subsequent treatment with butyl-lithium, trialkylborane and iodine;
reviewed by W. Carruthers [4] (Cont.)
Et-Mg+Br

C6H13 H Cu
..
C6H13 C C H C C:- ; Me S Me + Cu+ + Br-
.. ..
-
Me S+ Me + Br = CuBr.Me2S
Et
2-butyne +2 -
+ Mg + Br I-

C6H13 H .. C6H13 H C6H13 H

Me + Mg+2 +2 Br-
Et
C C + Me ..S
Et
C C
Cu
= Et
C C
CuMe2S.MgBr2
Cu
MgBr2
I+
..
Me S Me
..
C6H13 H MgBr2
C2H5 I C6H13 H C6H13 H
C C (C2H5)3B
C C C C-:
Et I Et Li + I2
I CuMe2S.MgBr2
- + C4H9-Li+ C4H9I
+ I CuMe2S.MgBr2

Li+
C6H13 Et
C6H13 H C6H13 H C6H13 H C2H5
C C Li +
C +
C Li +
C C Et C C
- - - H
Et BEt3 Et BEt3 Et BEt I BEt2
I+ I- Li+
I+ : ..I : .. : Et
: .. :

C6H13 Et C6H13 H
C2H5 C2H5 Et C6H13 H
C C C C C C + BIEt2 + LiI
H Et
I I Et
BEt2 B-Et2
I- Li+ I

Figure 13. Trisubstituted alkene synthesis by iodination and subsequent treatment with butyl-lithium, trialkylborane and iodine;
mechanistic views

The synthesis of trisubstituted alkenes can be achieved using allylic alcohols as starting material. This depends in
its critical phase on the stereoselective epoxidation of allylic alcohols. Hence, (Z)-6-methyl-5-undecene was obtained
by oxidation of the allylic alcohol 1 with t-butyl hydroperoxide and vanadium catalyst to selectively give rise to
erythro-epoxide 2 that at its turn was converted to the vicinal diol 3 thanks to interaction with lithium dibutylcuprate.
Stereospecific deoxygenation of the diol could be possible by interaction with N,N-dimethylformamide dimethyl
acetal. The dioxolane derivative obtained is then decomposed by heating and by adding acetic anhydride to give rise
to the Z-alkene [4]. The vanadium-t-butyl hydroperoxide react with the C=C of allylic alcohols making possible
selective epoxidations. Reaction of 1 with t-C4H9OOH in the presence of vanadium acetylacetonate as catalyst gave 2
almost exclusively [4,9,10]. See Figures 14 and 15.
CH H H3C
C4H9 C4H9 O Li(C4H9)2Cu C4H9 5 11 OH(CH3)2NCH(OCH3)2, 25oC C4H9 C5H11
t-C4H9OOH (CH3CO)2O
C4H9 C5H11
VO(acac)2 H o
ether, -26 C H o
130 C
HO CH3 HO CH3 HO CH3 O O H CH3
1 2 3 N(CH3)2
H
Figure 14. Trisubstituted alkene synthesis from allylic alcohol; reviewed by W. Carruthers [4]

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REVISTA BOLIVIANA DE QUÍMICA Vol. 32, No.1, pp. 15-23, Ene./Abr. 2015
Bolivian Journal of Chemistry 31(2) 15-23, Jan./Apr. 2015
Received 03 23 2015 Accepted 04 15 2015 Published 04 30 2015
Bravo et Vila .

O O O CH2 O CH2 CH2 O

acac : CH3 C CH2 C CH2- CH3 C CH2 C O -
VO(acac)2 : CH3 C CH2 C O V O C CH2 C CH3
O
t-bu (acac)2OV t-bu (acac)2OV t-bu (acac)2OV t-bu
O .. O O
+ .. O
O O.. O +O

..
H VOacac2 H H H
H H H H H H
_ H H

..
CH3 = CH3 CH3 CH3 =
HO HO HO HO
H H H H
_ .. C4H9
_ _ .. t-bu .. t-bu
..

..
O HO O
(acac)2OV t-bu .. ..
..

.. O.. + .. erythro
+O (acac)2OV O (acac)2OV O HO H
H .. H ..
CH3
H H

=
H H
C4H9 O
H H Li+ , Cu+
CH3 =
CH3
= H (C4H9)2-
HO HO HO CH3 HO CH3
H H H

H
.. H H.. _ C4H9
O
.. O Li+ C5H11 Li+O-
..

.. C4H9 C5H11 C4H9

O- +
C5H11
H Li =
C4H9 = = H =
H HO H
HO HO
CH3 CH3 HO O- +CH3 HO CH3
H H Li CH3
C4H9-
H
C4H9 C4H9 C4H 9 OCH3 O+CH3
C5H11 OLi C5H11 OLi C5H11 OH CH3 CH3
OCH3 H+ OCH3
OH H 2O OH N N

..
..

+ LiOH +
H OH CH3 H CH3 H
H CH H CH
=
CH3 3 3
+
C5H11
C4H9
C5H11 C5H11 C5H11 C5H11 OH
C4H9 C4H9 C4H9 C4H 9
CH3 CH3 CH3 CH3 H
H H H H HO CH3
HO H+O
..

..

HO + HO
..

OH O H +
..

..

O O +
..

..

..

..
NMe2 NMe2 MeOH H MeOH
CH3O H CH3O Me2N Me2N H
H O+HCH3
H O+CH3

C4H9 C5H11 C5H11 C5H11

CH3 C4H9 C4H9
H O O- C5H11 HO
C4H9
+ + O
..

H O -H +
(CH3CO)2O H
..

O +
..

H Me NMe2 H Me +
MeOH O NMe2 H Me O NMe2
Me2N H H

Figure 15. Trisubstituted alkene synthesis from allylic alcohol; mechanistic views

ACKNOWLEDGEMENTS

The authors express their gratitude to Prof. Eduardo Palenque from the Department of Physics, Universidad Mayor
de San Andrés, for his bibliographic support.

REFERENCES

1. Bravo, J. 2005, Bol. J. of Chem., 23, 1-10. (http://www.bolivianchemistryjournal.org, 2005).

Downloadable from: Revista Boliviana 22 de Química. Volumen 31 Nº2. Año 2014

http://www.bolivianchemistryjournal.org, http://www.scribd.com/bolivianjournalofchemistry
REVISTA BOLIVIANA DE QUÍMICA Vol. 32, No.1, pp. 15-23, Ene./Abr. 2015
Bolivian Journal of Chemistry 31(2) 15-23, Jan./Apr. 2015
Received 03 23 2015 Accepted 04 15 2015 Published 04 30 2015
Bravo et Vila .

2. Bravo, J.A., Mollinedo, P., Peñarrieta, J.M., Vila, J.L. 2013, Bol. J. of Chem., 30, 24-41
(http://www.bolivianchemistryjournal.org, 2013)
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Downloadable from: Revista Boliviana 23 de Química. Volumen 31 Nº2. Año 2014

http://www.bolivianchemistryjournal.org, http://www.scribd.com/bolivianjournalofchemistry