One-pot oxidation and Wittig olefination of alcohols using o-iodoxybenzoic acid and stable Wittig ylide

Article abstract of DOI:10.1081/SCC-100104061

Benylic, allylic, and propargylic alcohols, as well as diols, can be oxidized with o-iodoxybenzoic acid (IBX) in the presence of stabilized Wittig ylide to generate α,β-unsaturated ester in one pot. This is useful when the intermediate aldehydes are unsta

Full text of DOI:10.1081/SCC-100104061

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ONE-POT OXIDATION AND
WITTIG OLEFINATION
OF ALCOHOLS USING O-
IODOXYBENZOIC ACID AND
STABLE WITTIG YLIDE*
Arup Maiti a & J. S. Yadav b
a Organic Division , Indian Institute of Chemical
Technology , Hyderabad, 500007, India
b Organic Division , Indian Institute of Chemical
Technology , Hyderabad, 500007, India
Published online: 02 Aug 2010.
To cite this article: Arup Maiti & J. S. Yadav (2001) ONE-POT OXIDATION AND
WITTIG OLEFINATION OF ALCOHOLS USING O-IODOXYBENZOIC ACID AND STABLE
WITTIG YLIDE* , Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 31:10, 1499-1506, DOI: 10.1081/
SCC-100104061
To link to this article: http://dx.doi.org/10.1081/SCC-100104061
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SYNTHETIC COMMUNICATIONS, 31(10), 1499–1506 (2001)
ONE-POT OXIDATION AND WITTIG
OLEFINATION OF ALCOHOLS USING
O-IODOXYBENZOIC ACID AND
STABLE WITTIG YLIDE*
{
Arup Maiti and J.S.Yadav
Organic Division, Indian Institute of
Chemical Technology, Hyderabad-500007, India
ABSTRACT
Benylic, allylic, and propargylic alcohols, as well as diols, can
be oxidized with o-iodoxybenzoic acid (IBX) in the presence
of stabilized Wittig ylide to generate a,b-unsaturated ester in
one pot. This is useful when the intermediate aldehydes are
unstable and difficult to isolate.
The oxidation of primary alcohols to reactive aldehydes and their
subsequent homologation using stabilized Wittig ylide1 is a useful and
common step in synthetic organic chemistry (Eq. 1). Problems arise when
the intermediate aldehydes are inductively destabilized by strongly electro-
negative substituents, leading to hydration, decomposition,2,3 polymeriza-
tion4 or difficulty in isolating due to volatility and toxicity. Such problems
can be overcome by preparing the aldehydes and reacting them in situ with
stabilized ylide to give a,b-unsaturated esters.
* IICT communication no. 4369.
{ Corresponding author. Fax þ91-40-7170512; E-mail: yadav@iict.ap.nic.in
1499
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

1500
MAITI AND YADAV
Equation 1.
Several recent publications have highlighted the advantage of one-pot
oxidation-Wittig reaction under different conditions. These include Swern
oxidation5 active manganese dioxide oxidation,6 barium permanganate
oxidation,7 in the presence of ylide in the reaction mixture. Another
report by Barrett’s group8 used Dess-Martin periodinane (DMP) ([12-I-5]
species)9 for a similar process.
Inexpensive o-iodoxybenzoic acid (IBX) ([10-I-4] species)11 which is
used to prepare expensive DMP is itself a very efficient oxidizing agent.12–18
A number of applications of this reagent have emphasized its generality as a
mild oxidizing agent, as well as its ability to perform delicate transforma-
tions.12–18 In particular, IBX oxidizes vic-diols without cleaving the glycol
C-C bond12 and is stable to moisture. The oxidation can be performed in an
open flask without any particular precaution, such as inert atmosphere and
dry solvent.12
To utilize this characteristic of IBX, we report the oxidation of pri-
mary alcohols by IBX in the presence of stabilized ylide to trap the unstable
intermediate aldehydes, before they decompose or isomerize, to yield the
corresponding a,b-unsaturated ester at room temperature.
To demonstrate its utility and functional group compatibility, we
successfully carried out the oxidation, followed by olefination of aldehydes
derived from a wide variety of substrates, such as benzylic, allylic, and
propargylic alcohols and diols with (carboethoxymethylene)tripheyl-
phosporane, to obtain the corresponding a,b-unsaturated ester in good
yields, as shown in Table 1.
Propargyl alcohol 11 gave ynenote 12 in good yield. The inter-
mediate aldehyde, propynal, is a lachrymator and has a tendency to poly-
merize easily in basic medium. Even 1,2-diols as in ethylene glycol
15 produced diester 16 in very high yield. The oxidation of 1,2-diols itself
is very difficult to achieve by a method operable in the laboratory. In the case
of the allyl alcohols 5 and 9, the reaction proceeded with retention
of E-alkene geometry and alcohol 7 retained its Z-alkene geometry.
Only cinnamyl alcohol 3 underwent very slow oxidation-Wittig reaction.
All the products obtained (as shown in Table 1) were major in E-alkene
product (above 90%).

ALCOHOL OXIDATION
1501
Table 1. IBX Oxidation of Alcohols in the Presence of Wittig Ylide at Room
Temperature
Entry
no.
Time Yield
(%)
Alcohols
Products
(h)
1.
1.5
98
(1)
(3)
(2)
(4)
2.
3.
48
65
90
6
(5)
(7)
(9)
(6)
(8)
4.
5.
6.
7.
10
10
10
10
95
90
85
80
(10)
(11)
(13)
(12)
(14)
8.
9.
8
8
70
80
(15)
(17)
(16)
(18)
10.
8
80
(19)
(20)

1502
MAITI AND YADAV
In conclusion, the present procedure is a very efficient method for
homologation of unstable aldehydes. The significiant advantages offered
by this procedure are: a) inexpensive reagent; b) general application (effec-
tive for all types of primary alcohols); c) mild and neutral conditions (room
temperature, no inert or dry atmosphere or solvent needed); d) easy work-
up; e) high yield; and f ) environmentally friendly reaction (no toxic reagent).
Certainly this method offers a practical alternative to the existing
procedures.
EXPERIMENTAL
Melting points were recorded on a Buchi R-535 apparatus. IR spectras
were recorded on a Perkin-Elmer Infrared 683 spectrophotometer with
1
NaCl optics. H and 13C NMR spectra were recorded on Varian Gemini
200 MHz spectrometer. The samples were recorded in CDCl3 using tetra-
methysilane as the internal standard and are given on the ꢀ-scale. Mass mea-
surements were carried out on either Fnnigan-MAT1020Bor MicroMass
VG70-70H mass spectrometer operating at 70 eV using direct inlet system
and are given in the mass units (m/z). TLC was performed on 0.25-mm
E.Merk precoated silicagel plate (60F-254). All products were purified by
column chromatography on silicagel (100–200 mesh).
General Procedure
To a solution of alcohol (1.0 mmol) in dimethylsulfoxide (5 mL), a
mixture of (carboethoxy-methylene)triphenylphosphorane (1.5 mmol) and
iodoxybenzoic acid (1.5 mmol) was added and the reaction mixture stirred
at room temperature. After a few minutes, IBX was dissolved and the
solution turned orange-brown and hot. The resulting mixture was stirred
until TLC indicated the completion of reaction. After that, 10 mL water
was added and stirred for 5 m. Solid precipitate was filtered through
a celite pad and filtrate was extracted with ether (2ꢀ25 mL). Ether solu-
tion was concentrated in vacuum. The residue was chromatographed on
silica gel.
Ethyl cinnamate (Entry 1)19
Color1ess oil; TLC Rf 0.85 (hexane:Ethylacetate 4:1); IR (neat) ꢁ 1714,
1638, 1450, 1366, 1312, 1270, 1204, 1178, 769 cmꢁ1. EI-MS m/z 176 (Mþ).

ALCOHOL OXIDATION
1503
Ethyl 5-phenyl-2(E),4(E)-pentadienoate (Entry 2)
Colorless oil (lit.20 m.p. 25ꢂ–26ꢂC); TLC Rf 0.4 (hexane:Ethylacetate
9:1); IR (neat) ꢁ 3026, 2981, 1707, 1626, 1341, 1314, 1297, 1239, 1133, 1037,
998, 775, 714, 689 cmꢁ1 1H NMR (200 MHz, CDCl3) ꢀ 1.30(3H, t,
.
J ¼ 7.0 Hz), 4.23(2H, q, J ¼ 7.0 Hz), 5.99(1H, d, J ¼ 18.0 Hz), 6.80–7.60
(7H, m), 7.55(1H, d, J ¼ 18.0 Hz); 13C NMR (200 MHz, CDCl3) ꢀ 167.3,
144.6, 140.5, 136.4, 129.3, 128.9, 127.4, 126.5, 121.5, 60.5, 14.5; EI-MS
m/z 202(Mþ). Anal. calc. for C13H14O2: C, 77.20; H, 6.98. Found C,
76.96; H, 6.88.
Ethyl 5,9-dimethyl-2(E),4(E),8-decatrienoate (Entry 3)
Colorless oil (lit.21 bp. 103ꢂ–105ꢂC/0.5 mHg); TLC Rf 0.8
(hexane:Ethylacetate 4:1); IR (neat) ꢁ 2911, 2890, 1727, 1640, 1610, 1420,
1355, 1232, 1102, 1065, 1024, 990, 764 cmꢁ1. 1H NMR (200 MHz, CDCl3) ꢀ
1.29(3H, t, J ¼ 7.0 Hz), 1.61(3H, br.s), 1.68(3H, br.s), 1.89(3H, br.s),
2.1–2.2(4H, m), 4.20(2H, q, J ¼ 7.0 Hz), 4.80–5.20(1H, m), 5.78(1H, d,
J ¼ 18.0 Hz), 5.99(1H, br.d, J ¼ 18.0 Hz), 7.58(1H, dd, J ¼ 18.0, 12.0 Hz);
13C NMR (200 MHz, CDCl3) ꢀ 167.8, 149.6, 140.9, 132.2, 123.4, 123.3,
118.9, 60.0, 40.2, 26.3, 25.6, 17.6, 17.3, 14.3; EI-MS m/z 222(Mþ). Anal.
calc. for C14H22O2: C, 75.63; H, 9.97. Found C, 75.65; H, 9.86.
Ethyl 6-benzyloxy-2(E),4(Z)-hexadienoate (Entry 4)
Colorless oil. TLC Rf 0.82 (hexane:Ethylacetate 4:1); IR (neat) ꢁ 1991,
1755, 1648, 1455, 1350, 1140, 1110, 982, 853, 765, 720 cmꢁ1 1H NMR
.
(200 MHz, CDCl3) ꢀ 1.30(3H, t, J ¼ 7.0 Hz), 4.20(4H, m), 4.51(2H, s
J ¼ 7.0 Hz), 5.99(2H, m), 6.20(1H, m), 7.31(5H, m), 7.49(1H, m);
13C NMR (200 MHz, CDCl3) ꢀ 166.6, 141.4, 139.1, 133.5, 128.3, 127.8,
127.7, 127.6, 123.7, 69.6, 65.9, 60.7, 14.3; FABMS m/z 247(MþH)þ Anal.
calc. for C15H18O3: C, 73.17; H, 7.31. Found C, 73.18; H, 7.40.
Diethyl octa-2(E),4(E),6(E)-triene-dioate (Entry 5)
White crystals, m.p. 86ꢂC (pentane-ether) (lit.22 88ꢂ–89ꢂC); TLC
Rf 0.55 (hexane:Ethylacetate 5:1); IR (KBr) ꢁ 1711, 1627, 1370, 1340,
1300, 1236, 1134, 1026, 866 cmꢁ1 1H NMR (200 MHz, CDCl3) ꢀ 1.33
.
(6H, t, J ¼ 7.0 Hz). 4.20(2H, q, J ¼ 7.0 Hz), 6.00(2H, d, J ¼ 18.0 Hz),

1504
MAITI AND YADAV
6.60(2H, dd, J ¼ 3.0, 7.0 Hz), 7.30(2H, ddd, J ¼ 3.0, 7.0, 17.0 Hz); 13C NMR
(200 MHz, CDCl3) ꢀ 166.4, 142.7, 136.9, 124.7, 60.6, 14.3; FABMS m/z
225(MþH)þ. Anal. calc. for C12H16O4: C, 64.28; H, 7.14. Found C,
64.29; H, 7.16.
Ethyl 2(E)-penten-4-ynoate (Entry 6)23
Colorless oil; TLC Rf 0.8 (hexane:Ethylacetate 4:1); IR (neat) ꢁ 3293,
3262, 2101, 1725, 1259, 1170, 1039, 963 cmꢁ1; 1H NMR (200 MHz, CDCl3) ꢀ
1.31(3H, t, J ¼ 7.0 Hz), 2.29(1H, d, J ¼ 3.0 Hz), 4.21(2H, q, J ¼ 7.0 Hz),
6.29(1H, d, J ¼ 18.0 Hz), 6.69(1H, dd, J ¼ 3.0, 17.0 Hz); 13C NMR
(200 MHz, CDCl3) ꢀ 165.5, 132.6, 123.9, 85.9, 80.4, 60.9, 14.2. EI-MS
m/z 124 (Mþ). Anal. calc. for C7H8O2: C, 67.77; H, 6.45. Found C, 67.78;
H, 6.50.
Ethyl 2(E)-decane-4-ynoate (Entry 7)
Colorless oil; TLC Rf 0.8 (hexane:Ethylacetate 4:1); IR (neat) ꢁ 3218,
2929, 2903, 2832, 2201, 2112, 1715, 1618, 1460, 1366, 1299, 1176, 1155, 1035,
961 cmꢁ1
;
1H NMR (200 MHz, CDCl3)
ꢀ
0.90(3H, t, J ¼ 7.0 Hz),
11.2–1.6(8H, m), 2.35(2H, m), 4.20(2H, q, J ¼ 7.0 Hz), 6.10(1H, d,
J ¼ 18.0 Hz), 6.72(1H, d, J ¼ 18.0 Hz); 13C NMR (200 MHz, CDCl3) ꢀ
129.2, 126.0, 100.6, 78.2, 60.2, 31.2, 77.9, 60.3, 30.9, 27.9, 22.1, 19.9, 14.1,
13.8; EI-MS m/z 194 (Mþ). Anal. calc. for C12H18O2: C, 74.23; H, 9.28.
Found C, 74.18; H, 9.26.
Diethyl hexa-2(E),4(E)-diene-1,6-dioate (Entry 8)
White crystals, m.p. 60ꢂC (pentane-ether) (lit.24 63ꢂ–64ꢂC); TLC Rf
0.55 (hexane:Ethylacetate 5:1); IR (KBr) ꢁ 1699, 1612, 1254, 1172, 1025,
866 cmꢁ1. 1H NMR (200 MHz, CDCl3) ꢀ 1.31(6H, t, J ¼ 7.0 Hz), 4.20(2H, q,
J ¼ 7.0 Hz), 6.15–6.30(2H, m), 7.20–7.38(2H, m); 13C NMR (200 MHz,
CDCl3) ꢀ 165.9, 140.8, 128.4, 60.9, 14.3; FABMS m/z 199(MþH)þ. Anal.
calc. for C10H14O4: C,60.60; H, 7.07. Found C, 60.61; H, 7.07.
Diethly octa-2(E),6(E)-diene-1,6-dioate (Entry 9)25
Colorless oil; TLC Rf 0.43 (hexane:Ethylacetate 5:1); IR (neat) ꢁ 2930,
2910, 2850, 1724, 1655, 1392, 1300, 1254, 1142, 1112, 1042, 993, 770 cmꢁ1
.

ALCOHOL OXIDATION
1505
1H NMR (200 MHz, CDCl3) ꢀ 1.30(6H, t, J ¼ 7.0 Hz), 2.37(4H, d,
J ¼ 7.0 Hz), 4.17(4H, q, J ¼ 7.0 Hz), 5.80(2H, d, J ¼ 18.0 Hz), 6.91(2H, dt,
J ¼ 7.0, 17.5 Hz); 13C NMR (200 MHz, CDCl3) ꢀ 166.3, 146.8, 122.3, 60.2,
30.4, 14.3: MS m/z 227(MþH)þ. HRMS for C12H19O4(MþH)þ 227.1287
calc. for 227.1283.
Ethyl 6-benzyloxy-2(E)-hexenoate (Entry 10)
Colorless oil; TLC Rf 0.43 (hexane:Ethylacetate 5:1); IR (neat) ꢁ 2925,
2701, 2660, 1725, 1642, 1440, 1332, 1286, 1221, 1181, 1102, 1035, 977,
760 cmꢁ1
.
1H NMR (200 MHz, CDCl3) ꢀ 1.29(3H, t, J ¼ 7.0 Hz), 1.75
(2H, m), 2.30(2H, m), 3.45(2H, m), 4.17(4H, q, J ¼ 7.0 Hz), 4.45(2H, s,
J ¼ 7.0 Hz), 5.79(1H, d, J ¼ 18.0 Hz) 6.91(1H, dt, J ¼ 7.0, 17.5 Hz),
7.25(5H, m); 13C NMR (200 MHz, CDCl3) ꢀ 166.5, 149.4, 139.4, 129.3,
127.5, 121.7, 72.9, 69.7, 60.0, 53.1, 29.7, 29.1, 14.7; MS m/z 249 (MþH)þ.
Anal. calc. for C15H20O3: C, 72.58; H, 8.06. Found C, 72.59; H, 8.01.
CAUTION
IBX has been reported to detonate26 upon heavy impact and heating
over 200ꢂC. Dess and Martin reported9,10 that heating and striking IBX
with a hammer did not cause any detonation. In our hands, we observed
no hazard using IBX at room temperature.
ACKNOWLEDGMENTS
One of the authors (AM) is thankful to CSIR, New Delhi, for
awarding Research Fellowship.
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MAITI AND YADAV
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Received in the UK April 4, 2000