Facile oxidation of alcohols to aldehydes or ketones with 1-acetoxy-5-nitro-1,2-benziodoxole-3(1 H)-one

Article abstract of DOI:10.1055/s-0033-1339283

Various benzylic alcohols and aliphatic secondary alcohols were smoothly oxidized to the corresponding aromatic aldehydes, aromatic ketones, and aliphatic ketones, respectively, with the novel 1-acetoxy-5-nitro-1,2- benziodoxole-3(1H)-one (ANBX) alone, a trivalent iodine prepared from the oxidation of 2-iodo-5-nitrobenzoic acid with MCPBA. The present reaction is the first effective method for the oxidation of alcohols with a trivalent iodine alone under mild reaction conditions. Georg Thieme Verlag Stuttgart New York.

Full text of DOI:10.1055/s-0033-1339283

LETTER
▌1707
lFettaercile Oxidation of Alcohols to Aldehydes or Ketones with 1-Acetoxy-5-nitro-
1
,2-benziodoxole-3(1H)-one
Facile Oxidation with 1-Acetoxy-5-nitro-1,2-benziodoxole-3(1H)-one
Masataka Iinuma, Katsuhiko Moriyama, Hideo Togo*
Graduate School of Science, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522, Japan
Fax +81(43)2902792; E-mail: togo@faculty.chiba-u.jp
Received: 26.04.2013; Accepted after revision: 21.05.2013
5c
eties–peracetic acid system, and a bifunctional hybrid-
type catalyst bearing TEMPO and an iodobenzene moi-
ety–peracetic acid system was reported. However, there
Abstract: Various benzylic alcohols and aliphatic secondary alco-
hols were smoothly oxidized to the corresponding aromatic alde-
hydes, aromatic ketones, and aliphatic ketones, respectively, with
5
d
the novel 1-acetoxy-5-nitro-1,2-benziodoxole-3(1H)-one (ANBX) are still certain drawbacks, such as the addition to the car-
alone, a trivalent iodine prepared from the oxidation of 2-iodo-5- bon–carbon double bond of the substrates by bromonium
nitrobenzoic acid with MCPBA. The present reaction is the first
effective method for the oxidation of alcohols with a trivalent iodine
alone under mild reaction conditions.
ion species, the reusability and availability of the reagents,
and the oxidation to carboxylic acids. Here, we would like
to report the oxidation of alcohols to aldehydes or ketones
Key words: 1-acetoxy-5-nitro-1,2-benziodoxole-3(1H)-one, oxi-
dation, alcohol, aldehyde, ketone
with the novel trivalent iodine reagent, 1-acetoxy-5-nitro-
6
1
,2-benziodoxol-3(1H)-one (ANBX), alone.
ANBX was easily prepared in good yield by the oxidation
of 2-iodo-5-nitrobenzoic acid with m-chloroperoxybenzo-
ic acid (MCPBA) using our previous method, as shown
Recently, hypervalent iodines have received considerable
attention for possible use in organic synthesis due to their
nonmetallic nature and low toxicity, which make them en-
vironmentally benign, as well as their excellent oxidation
7
in Scheme 1. To establish the best reaction conditions, the
oxidation of p-methylbenzyl alcohol with ANBX (1.2
equiv, 1.5 equiv, and 2.0 equiv) was carried out at room
temperature and 65 °C for 12 hours and 24 hours, respec-
tively, in N,N-dimethylformamide (DMF) due to the mod-
erate solubility in DMF, and p-tolualdehyde was obtained
in good yield with 1.5 equivalents or 2.0 equivalents of
1
ability and high chemoselectivity. Dess–Martin periodi-
nane
[1,1,1-triacetoxy-1,1-dihydro-1,2-benziodoxol-
2
3(1H)-one] and 1-hydroxy-1,2-benziodoxol-3(1H)-one
3
(
2-iodoxybenzoic acid; IBX) are examples of pentavalent
iodines [I(V)] that are used for the efficient oxidation of
alcohols. Dess–Martin periodinane, in particular, is the
best reagent for the selective oxidation of alcohols to alde-
hydes or ketones because the reaction can be carried out
in dichloromethane typically at room temperature. How-
ever, Dess–Martin periodinane and IBX are heat- and
shock-sensitive reagents and therefore, all experimental
operations must be conducted behind an explosion
shield.2c Recently, the 2,2,6,6-tetramethylpiperidine-1-
oxyl (TEMPO)-catalyzed oxidation of alcohols to alde-
hydes or ketones with (diacetoxyiodo)benzene (DIB) has
ANBX at 65 °C for 24 hours, as shown in Table 1 (entries
8
1–5). When the effect of solvents, namely, DMF, dichlo-
romethane, chloroform, tetrahydrofuran (THF), aceto-
nitrile, dimethyl sulfoxide (DMSO), and N,N-
dimethylacetamide (DMA), was compared, DMF was
found to have the best reactivity, giving p-tolualdehyde in
good yield (entries 4–11). This is due to the moderate sol-
ubility of ANBX in DMF. On the other hand, the solubil-
ity of ANBX in dichloromethane, chloroform, THF, and
acetonitrile is quite low. Thus, typical aprotic polar sol-
vents, such as DMF, showed high reactivity, and DMSO
and DMA showed similar reactivity to give p-tolualde-
hyde in good yields. However, DMF gave a slightly better
result than DMSO or DMA (entries 4, 10, and 11).
4
become very popular in organic synthesis. In this case,
the reactive species for the oxidation of alcohols is a nitro-
sonium derivative that is formed by the oxidation of
TEMPO with DIB, and the aldehyde or ketone in the re-
action mixture is purified by column chromatography to
remove iodobenzene, a co-product. Recently, the oxida-
tion of alcohols to aldehydes or ketones with a 1-(4′-di-
acetoxyiodobenzene)-3-methylimidazolium tetrafluoro-
I
AcO
I
O
COOH
O
MCPBA (1.1 equiv)
AcOH, 60 °C, 48 h
5
a
borate–KBr–[emim]BF system, a 1-(4′-diacetoxyiodo-
4
NO2
benzene)-3-methylimidazolium tetrafluoroborate–3-methyl-
NO2
5
b
imidazolium-supported TEMPO–water system,
a
ANBX
bifunctional catalyst bearing an ionic-liquid-supported
(
2,2,6,6-tetramethylpiperidin-1-yl)oxyl, iodoarene moi- Scheme 1 Preparation of ANBX
Another notable advantage of the present oxidation meth-
od is that the product can be obtained in good yield with
high purity by diethyl ether–hexane (1:1) extraction of the
SYNLETT 2013, 24, 1707–1711
Advanced online publication: 28.06.2013
0
9
3
6
-
5
2
1
4
1
4
3
7
-
2
0
9
6
DOI: 10.1055/s-0033-1339283; Art ID: ST-2013-U0386-L
Georg Thieme Verlag Stuttgart · New York
©

1708
M. Iinuma et al.
LETTER
Table 1 Optimization of Reaction Conditions
nol, 1-phenyl-1-nonanol, and diphenylmethanol, were
treated with ANBX under the same conditions to provide
the corresponding aromatic aldehydes and aromatic ke-
tones in good yields with high purity (entries 1, 3, 5 and
ANBX ( X equiv)
OH
O
solvent, temp, time
7–14). Reuse of the recovered and regenerated ANBX for
Entry
X
Solvent
Temp. Time
Yielda
Purityb
the oxidation of 4-methylbenzyl alcohol, 4-chlorobenzyl
alcohol, and piperonyl alcohol in DMF under the same
conditions gave 4-methylbenzaldehyde, 4-chlorobenzal-
dehyde, and piperonal in good yields with high purity, re-
spectively (entries 2, 4, and 6). Moreover, cinnamyl
alcohol, 1-adamantamethanol which is an aliphatic prima-
ry alcohol, borneol, cyclododecanol, and β-cholestanol
which are secondary alcohols, could be also oxidized to
the corresponding aldehydes and aliphatic ketones in
good yields with high purity (entries 15–19). 2,3,4,6-Tet-
ra-O-benzyl-D-glucose could be also oxidized to the cor-
responding lactone in good yield with high purity (entry
1
2
3
4
5
6
7
8
9
1.2
1.2
1.2
1.5
2.0
1.5
1.5
1.5
1.5
1.5
1.5
DMF
DMF
DMF
DMF
DMF
CH Cl
r.t.
12 h
12 h
24 h
24 h
24 h
24 h
24 h
24 h
24 h
24 h
24 h
52%
71%
78%
87%
97%
18%
23%
4%
36%
62%
71%
84%
98%
16%
21%
3%
65 °C
65 °C
65 °C
65 °C
38 °C
65 °C
65 °C
65 °C
65 °C
65 °C
2
2
CHCl3
THF
20). Thus, various benzylic alcohols and secondary alco-
hols could be smoothly oxidized to the corresponding ar-
omatic aldehydes, aromatic ketones, and aliphatic ketones
by the treatment with ANBX in DMF and the products
could be obtained in good yields with good to high purity
by simple extraction of the reaction mixture with diethyl
ether–hexane (1:1) and subsequent removal of the solvent.
However, primary aliphatic alcohols, such as 3-phenyl-1-
propanol and 1-octanol, could not be oxidized to the cor-
responding aldehydes at all, and the alcohols were recov-
MeCN
DMSO
DMA
6%
4%
1
1
0
1
84%
82%
83%
80%
a
Purified yield.
b
Purity after extraction of the reaction mixture with Et O–hexane and
removal of the solvent.
2
reaction mixture from a weakly basic aqueous solution ered in high yields. Therefore, when a mixture of
(
NaHCO ) and subsequent removal of the solvent. 2-Iodo- cyclododecanol (1.0 mmol) and 1-octanol (1.0 mmol) in
3
5
-nitrobenzoic acid, the co-product, could be recovered in DMF was treated with ANBX (2.0 mmol) for 24 hours at
9
2% yield by filtration of the acidified (pH ca. 2) aqueous 65 °C, cyclododecanone was obtained in 74% yield, to-
solution with 1 M aqueous HCl. Once 2-iodo-5-nitroben- gether with 1-octanol in 98% yield.
zoic acid was recovered by the filtration, ANBX could be
In conclusion, the present oxidation reaction with ANBX
is the first method for the effective oxidation of benzylic
regenerated in 94% yield by oxidation with MCPBA.
Based on these results, various benzylic alcohols and sec- alcohols and aliphatic secondary alcohols to aromatic al-
ondary alcohols were treated with ANBX in DMF for 24 dehydes, aromatic ketones, and aliphatic ketones, respec-
hours at 65 °C to provide the corresponding aldehydes or tively, with a trivalent iodine reagent alone under mild
ketone in good yields with good to high purity, as shown reaction conditions. ANBX is expected to become a good
in Table 2. Benzylic alcohols, such as 4-chlorobenzyl al- reagent for the oxidation of alcohols to aromatic alde-
cohol, piperonyl alcohol, 4-phenylbenzyl alcohol, 4-allyl- hydes, aromatic ketones, and aliphatic ketones, respec-
oxybenzyl
alcohol,
2-thiophenemethanol,
3- tively. Further synthetic study of ANBX is underway in
pyridinemethanol, and 2-benzothiophenemethanol, and this laboratory.
secondary benzylic alcohols, such as 1-phenyl-1-propa-
Table 2 Oxidation of Alcohols to Aldehydes or Ketones with ANBX
ANBX ( 2.0 equiv)
alcohols
aldehydes or ketones
DMF, 65 °C, 24 h
Entry
Aldehyde or Ketone
Yielda
Purityb
1
2
O
97%
98%
95%c
96%c
O
3
4
93%
93%
92%c
93%c
Cl
O
5
6
O
92%
92%
91%c
92%c
O
Synlett 2013, 24, 1707–1711
© Georg Thieme Verlag Stuttgart · New York

LETTER
Facile Oxidation with 1-Acetoxy-5-nitro-1,2-benziodoxole-3(1H)-one
1709
Table 2 Oxidation of Alcohols to Aldehydes or Ketones with ANBX (continued)
ANBX ( 2.0 equiv)
alcohols
aldehydes or ketones
DMF, 65 °C, 24 h
Entry
Aldehyde or Ketone
Yielda
91%
Purityb
91%
O
7
Ph
O
8
9
90%
90%
O
O
98%
86%
97%
98%
85%
97%
S
N
O
1
0
1
O
1
S
O
O
O
1
1
1
1
2
3
4
5
87%
86%
89%
89%
86%
86%
89%
90%
O
O
1
6
7
88%
74%
87%
73%
O
1
O
1
8
9
76%
75%
76%
75%
1
O
©
Georg Thieme Verlag Stuttgart · New York
Synlett 2013, 24, 1707–1711

1710
M. Iinuma et al.
LETTER
Table 2 Oxidation of Alcohols to Aldehydes or Ketones with ANBX (continued)
ANBX ( 2.0 equiv)
alcohols
aldehydes or ketones
DMF, 65 °C, 24 h
Entry
Aldehyde or Ketone
Yielda
84%
Purityb
83%
O
OBn
OBn
O
20
BnO
OBn
a
b
c
Purified yield.
Purity after extraction of the reaction mixture with Et O–hexane and removal of the solvent.
Recovered and regenerated ANBX was used.
2
Acknowledgement
de Kanter, F. J. J.; Groen, M. B.; Hanefeld, U.; Orru, R. V.
A. Eur. J. Org. Chem. 2006, 1672. (g) Fuwa, H.;
Yamaguchi, M.; Sasaki, M. Org. Lett. 2010, 12, 1848.
Financial support in the form of a Grant-in-Aid for Scientific Re-
search (No. 25105710) from the Ministry of Education, Culture,
Sports, Science, and Technology in Japan and the Iodine Research
Project in Chiba University is gratefully acknowledged.
(h) Uchiro, H.; Kato, R.; Arai, Y.; Hasegawa, M.;
Kobayakawa, Y. Org. Lett. 2011, 13, 6268. (i) Shimokawa,
J.; Harada, T.; Yokoshima, S.; Fukuyama, T. J. Am. Chem.
Soc. 2011, 133, 17634. (j) Reddy, C. R.; Rao, N. N.; Sujitha,
P.; Kumar, C. G. Eur. J. Org. Chem. 2012, 1819. (k) Guérin,
C.; Bellosta, V.; Guillamot, G.; Cossy, J. Eur. J. Org. Chem.
Supporting Information for this article is available online at
http://www.thieme-connect.com/ejournals/toc/synlett.SnoIufproig
m
iotSrat
n
ungIifoop
r
t
2
012, 2990. (l) Suzuki, Y.; Iinuma, M.; Moriyama, K.;
Togo, H. Synlett 2012, 23, 1250.
(
5) (a) Weixing, Q.; Erlei, J.; Weiliang, B.; Yongmin, Z. Angew.
Chem. Int. Ed. 2005, 44, 952. (b) Weixing, Q.; Erlei, J.;
Weiliang, B.; Yongmin, Z. Tetrahedron 2006, 62, 556.
(c) Zhu, C.; Yoshimura, A.; Wei, Y.; Nemykin, V. N.;
Zhdankin, V. V. Tetrahedron 2012, 53, 1438. (d) Yakura,
T.; Ozuno, A. Adv. Synth. Catal. 2011, 353, 855.
References and Notes
(1) For recent reviews, see: (a) Togo, H.; Katohgi, M. Synlett
2001, 565. (b) Zhdankin, V. V.; Stang, P. J. Chem. Rev.
2002, 102, 2523. (c) Stang, P. J. J. Org. Chem. 2003, 68,
2997. (d) Tohma, H.; Kita, Y. Adv. Synth. Catal. 2004, 346.
(
e) Moriarty, R. M. J. Org. Chem. 2005, 70, 2895. (f) Wirth,
(6) Experimental Procedure for the Preparation of 1-
Acetoxy-5-nitro-1,2-benziodoxol-3(1H)-one (ANBX): 2-
Iodobenzoic acid (5.0 mmol 1.24 g) was added to a solution
mixture of 1 M HNO (4 mL) and 1 M H SO (6 mL) slowly
T. Angew. Chem. Int. Ed. 2005, 44, 3656. (g) Richardson, R.
D.; Wirth, T. Angew. Chem. Int. Ed. 2006, 45, 4402.
(
h) Ochiai, M. Chem. Rev. 2007, 7, 12. (i) Zhdankin, V. V.;
3
2
4
Stang, P. J. Chem. Rev. 2008, 108, 5299. (j) Merritt, E. A.;
Olofsson, B. Angew. Chem. Int. Ed. 2009, 48, 9052.
at 0 °C. The reaction mixture was stirred for 30 min at r.t.
Then, the mixture was stirred for 3 h at 130 °C. After the
reaction was complete, the mixture was added to ice-water
(30 mL), and the obtained mixture was filtered to afford 2-
iodo-5-nitrobenzoic acid in 85% yield. To a solution of 2-
iodo-5-nitrobenzoic acid (5.0 mmol 1.46 g) in AcOH (40
mL) was added MCPBA (6.0 mmol 1.59 g). The reaction
mixture was stirred for 48 h at 65 °C. After the reaction was
(
4
k) Ochiai, M.; Miyamoto, K. Eur. J. Org. Chem. 2008,
229. (l) Dohi, T.; Kita, Y. Chem. Commun. 2009, 2073.
(
(
m) Uyanik, M.; Ishihara, K. Chem. Commun. 2009, 2086.
n) Pouységu, L.; Deffieux, D.; Quideau, S. Tetrahedron
2
010, 66, 2235. (o) Zhdankin, V. V. J. Org. Chem. 2011, 76,
1185. (p) Merritt, E. A.; Olofsson, B. Synthesis 2011, 517.
(
q) Hypervalent Iodine Chemistry: Modern Developments in
Organic Synthesis, In Topics in Current Chemistry; Vol.
24; Wirth, T., Ed.; Springer: Berlin, 2003.
2) (a) Dess, D. S.; Martin, J. C. J. Org. Chem. 1983, 48, 4155.
b) Dess, D. S.; Martin, J. C. J. Am. Chem. Soc. 1991, 113,
277. (c) Boeckman, R. K. Jr.; Shao, P.; Mullins, J. J. Org.
complete, the reaction mixture was added to Et O (40 mL) at
2
0 °C, and the obtained mixture was filtered to afford 1-
acetoxy-5-nitro-1,2-benziodoxol-3(1H)-one in 95% (1.67 g)
yield. ANBX is not explosive below 200 °C.
2
(
(
7
1-Acetoxy-5-nitro-1,2-benziodoxol-3(1H)-one: mp 175–
–
1 1
179 °C. IR (neat): 1697, 1665, 1525, 1346 cm . H NMR
Synth., Coll. Vol. X 2004, 696. (d) Holsworth, D. D. Name
Reactions for Functional Group Transformations; Li, J. J.;
Corey, E. J., Eds.; John Wiley & Sons: Hoboken, 2007, 218.
3) (a) Corey, E. J.; Palani, A. Tetrahedron Lett. 1995, 36, 3485.
(500 MHz, DMF-d ): δ = 1.96 (s, 3 H), 8.26 (d, J = 8.9 Hz,
7
1 H), 8.67 (d, J = 2.3 Hz, 1 H), 8.78 (dd, J = 2.3, 2.6 Hz, 1
1
3
H). C NMR (125 MHz, DMF-d ): δ = 20.84, 125.52,
7
(
128.20, 128.81, 128.85, 134.31, 150.81, 166.82, 172.53.
(b) Frigerio, M.; Santagostino, M.; Sputore, S. J. Org. Chem.
HRMS (ESI): m/z [M + H] calcd for C H O NI: 351.9313;
9
7
6
1
999, 64, 4537. (c) Nicolaou, K. C.; Baran, P. S.; Zhong, Y.
found: 351.9320.
J. Am. Chem. Soc. 2001, 123, 3183.
(7) Iinuma, M.; Moriyama, K.; Togo, H. Synlett 2012, 23, 2663.
(8) Experimental Procedure for the Oxidation of Alcohols in
DMF: To a solution of 4-methylbenzyl alcohol (1.0 mmol,
122.1 mg) in DMF (4 mL) was added 1-acetoxy-5-nitro-1,2-
benziodoxol-3(1H)-one (2.0 mmol, 703.8 mg). The mixture
was stirred for 24 h at 65 °C. After the reaction was
(
4) (a) De Mico, A.; Margarita, R.; Parlanti, L.; Vescovi, A.;
Piancatelli, G. J. Org. Chem. 1997, 62, 6974. (b) Sakuratani,
K.; Togo, H. Synthesis 2003, 21. (c) But, T. Y. S.; Tashino,
Y.; Togo, H.; Toy, P. H. Org. Biomol. Chem. 2005, 3, 970.
(
(
d) Piancatelli, G.; Leonelli, F. Org. Synth. 2006, 83, 18.
e) Vatele, J. Tetrahedron Lett. 2006, 47, 715. (f) Vugts, D.
complete, the reaction mixture was added to aq NaHCO (10
3
J.; Veum, L.; al-Mafraji, K.; Lemmens, R.; Schmitz, R. F.;
mL). The aqueous layer was extracted with a mixture of
Synlett 2013, 24, 1707–1711
© Georg Thieme Verlag Stuttgart · New York

LETTER
Facile Oxidation with 1-Acetoxy-5-nitro-1,2-benziodoxole-3(1H)-one
1711
Et O–hexane (1:1; 3 × 10 mL). The organic layer was dried
H), 3.00 (q, J = 7.3 Hz, 2 H), 7.45 (t, J = 7.7 Hz, 2 H), 7.55
(t, J = 7.7 Hz, 1 H), 7.96 (d, J = 7.7 Hz, 2 H). C NMR (100
2
1
3
over Na SO and filtered. After removal of the solvent under
2
4
reduced pressure, 4-methylbenzaldehyde was obtained with
MHz, CDCl ): δ = 7.72, 31.25, 127.44, 128.02, 132.35,
136.39, 200.28.
3
1
98% purity. The purity was estimated by H NMR. The
–
1
purified 4-methylbenzaldehyde was obtained in 97% yield
by a flash short column chromatography on silica gel. On the
other hand, the aqueous layer was acidified (pH ca. 2) with
1-Phenylnonan-1-one: oil. IR (neat): 2924, 1685, 689 cm .
1
H NMR (400 MHz, CDCl ): δ = 0.88 (t, J = 6.0 Hz, 3 H),
1.23–1.38 (m, 10 H), 1.69–1.77 (m, 2 H), 2.92 (t, J = 7.3 Hz,
2 H), 7.41 (t, J = 6.7 Hz, 2 H), 7.50 (t, J = 6.7 Hz, 1 H), 7.94
3
1
M aq HCl (15 mL) and the obtained mixture was filtered
13
to afford 2-iodo-5-nitrobenzoic acid in over 92% yield.
ANBX could be easily obtained again by the oxidation of 2-
iodo-5-nitrobenzoic acid by MCPBA in over 94% yield.
(d, J = 8.3 Hz, 2 H). C NMR (100 MHz, CDCl ): δ = 13.86,
3
22.44, 24.24, 28.97, 29.15, 29.26, 31.62, 38.28, 127.75,
128.24, 132.53, 136.80, 199.92.
4
2
-Methylbenzaldehyde: oil (commercial, oil). IR (neat):
Benzophenone: mp 49–52 °C (commercial, mp 49 °C). IR
–
1
1
–1 1
827, 2734, 1702, 809 cm . H NMR (400 MHz, CDCl ): δ
(Nüjol): 1657 cm . H NMR (400 MHz CDCl ): δ = 7.48 (t,
3
3
=
2
2.44 (s, 3 H), 7.33 (d, J = 7.9 Hz, 2 H), 7.78 (d, J = 7.9 Hz,
J = 7.5 Hz, 4 H), 7.58 (t, J = 7.5 Hz, 2 H), 7.80 (d, J = 7.5
1
3
13
H), 9.97 (s, 1 H). C NMR (100 MHz, CDCl ): δ = 21.50,
Hz, 4 H). C NMR (100 MHz, CDCl ): δ = 128.20, 129.98,
3
3
1
4
4
29.33, 129.46, 133.81, 145.15, 191.62.
132.35, 137.51, 196.70.
-Chlorobenzaldehyde: mp 48–49 °C (commercial, mp
trans-Cinnamaldehyde: oil (commercial, oil). IR (neat):
–
1
1
–1 1
7–50 °C). IR (Nüjol): 2727, 1710 cm . H NMR (400
2816, 2743, 1676 cm . H NMR (400 MHz, CDCl ): δ =
3
MHz, CDCl ): δ = 7.52 (d, J = 8.4 Hz, 2 H), 7.83 (d, J = 8.4
6.72 (dd, J = 7.7, 16.1 Hz, 1 H), 7.41–7.46 (m, 3 H), 7.48 (d,
J = 16.1 Hz, 1 H), 7.54–7.60 (m, 2 H), 9.71 (d, J = 7.7 Hz, 1
3
13
Hz, 2 H), 9.98 (s, 1 H). C NMR (100 MHz, CDCl ): δ =
3
1
3
1
28.93, 130.36, 134.16, 140.39, 190.31.
H). C NMR (100 MHz, CDCl ): δ = 128.31, 128.42,
3
Piperoylaldehyde: mp 37–39 °C (commercial, mp 36–38
128.93, 131.09, 133.81, 152.60, 193.52.
–
1 1
°
C). IR (Nüjol): 2725, 1685 cm . H NMR (400 MHz,
1-Adamantanecarboxaldehyde: mp 140–142 °C. IR
–
1 1
CDCl ): δ = 6.07 (s, 2 H), 6.93 (d, J = 7.9 Hz, 1 H), 7.32 (d,
(Nüjol): 2815, 2698, 1722 cm . H NMR (400 MHz,
3
J = 1.6 Hz, 1 H), 7.41 (dd, J = 7.9, 1.6 Hz, 1 H), 9.80 (s, 1
CDCl ): δ = 1.68–1.80 (m, 12 H), 2.03–2.09 (m, 3 H), 9.32
3
13
13
H). C NMR (100 MHz, CDCl ): δ = 102.02, 106.77,
(s, 1 H). C NMR (100 MHz, CDCl ): δ = 27.31, 35.80,
3
3
1
08.24, 128.55, 131.77, 148.60, 153.00, 190.17.
36.52, 44.82, 206.09.
4
-Phenylbenzaldehyde: mp 57–58 °C (commercial, mp 58
Camphor: mp 170–173 °C (commercial, mp 172–180 °C).
–1
1
–1 1
°C). IR (Nüjol): 2726, 1708, 833 cm . H NMR (400 MHz,
IR (Nüjol): 1749 cm . H NMR (400 MHz, CDCl ): δ = 0.84
3
CDCl ): δ = 7.40 (t, J = 7.2 Hz, 1 H), 7.47 (t, J = 7.2 Hz, 2
(s, 3 H), 0.91 (s, 3 H), 0.96 (s, 3 H), 1.30–1.45 (m, 2 H), 1.68
(td, J = 12.5, 4.0 Hz, 1 H), 1.84 (d, J = 18.4 Hz, 1 H), 1.90–
2.00 (m, 1 H), 2.09 (t, J = 4.0 Hz, 1 H), 2.35 (dt, J = 18.4, 4.0
3
H), 7.62 (d, J = 7.2 Hz, 2 H), 7.73 (d, J = 8.2 Hz, 2 H), 7.93
(
d, J = 8.2 Hz, 2 H), 10.04 (s, 1 H). 13C NMR (100 MHz,
13
CDCl ): δ = 126.94, 127.26, 128.06, 128.60, 129.85, 134.77,
Hz, 1 H). C NMR (100 MHz, CDCl ): δ = 9.08, 18.98,
3
3
1
4
1
39.26, 146.74, 191.49.
19.61, 26.89, 29.75, 42.89, 43.14, 46.62, 57.53, 219.53.
-(Allyloxy)benzaldehyde: oil. IR (neat): 1686, 1596, 1251,
Cyclododecanone: mp 60–62 °C (commercial, mp 61 °C).
–
1
1
–1 1
157, 829 cm . H NMR (400 MHz, CDCl ): δ = 4.62 (d, J
IR (neat): 2928, 1702, 1470 cm . H NMR (500 MHz,
3
=
=
2
5.2 Hz, 2 H), 5.33 (dd, J = 10.6, 1.4 Hz, 1 H), 5.44 (dd, J
17.4, 1.4 Hz, 1 H), 6.01–6.10 (m, 1 H), 7.01 (d, J = 8.8 Hz,
H), 7.83 (d, J = 8.6 Hz, 2 H), 9.88 (s, 1 H). C NMR (100
CDCl ): δ = 1.24–1.34 (m, 14 H), 1.68–1.74 (m, 4 H), 2.46
3
13
(t, J = 6.2 Hz, 4 H). C NMR (100 MHz, CDCl ): δ = 21.99,
3
1
3
22.21, 23.87, 24.25, 24.40, 40.01, 212.46.
MHz, CDCl ): δ = 68.90, 114.89, 118.27, 129.91, 131.87,
5α-Cholestan-3-one: mp 123–125 °C (commercial, mp
128–129 °C). IR (Nüjol): 1719 cm . H NMR (400 MHz,
3
–1 1
1
32.18, 163.49, 190.71.>
2
-Thiophenecarboxaldehyde: oil (commercial, oil). IR
CDCl ): δ = 0.68 (s, 3 H), 0.69–0.76 (m, 1 H), 0.84–0.92 (m,
3
–1 1
(
neat): 2820, 2761, 1671 cm . H NMR (400 MHz, CDCl ):
9 H), 1.01 (s, 3 H), 0.94–1.18 (m, 9 H), 1.23–1.44 (m, 9 H),
1.46–1.60 (m, 4 H), 1.66–1.74 (m, 1 H), 1.78–1.89 (m, 1 H),
3
δ = 7.22 (dd, J = 4.8, 3.8 Hz, 1 H), 7.75–7.82 (m, 2 H), 9.95
1
3
13
(s, 1 H). C NMR (100 MHz, CDCl ): δ = 128.22, 135.03,
1.96–2.12 (m, 3 H), 2.21–2.44 (m, 3 H). C NMR (100
3
1
36.21, 143.94, 182.89.
MHz, CDCl ): δ = 11.43, 12.04, 18.64, 21.42, 22.53, 22.79,
3
–
1 1
Nicotinaldehyde: oil. IR (neat): 1699, 1588, 700 cm . H
NMR (400 MHz, CDCl ): δ = 7.50–7.54 (m, 1 H), 8.20 (d, J
=
23.79, 24.19, 27.98, 28.21, 28.95, 31.69, 35.36, 35.61,
35.76, 36.11, 38.17, 38.54, 39.47, 39.88, 42.56, 44.70,
46.68, 53.78, 56.23, 212.12.
3
8.8 Hz, 1 H), 8.87 (d, J = 8.6 Hz, 1 H), 9.10 (s, 1 H), 10.14
1
3
(s, 1 H). C NMR (100 MHz, CDCl ): δ = 123.45, 131.02,
2,3,4,6-Tetra-O-benzy-D-glucono-1,5-lactone: oil. IR
3
–
1
1
35.49, 151.55, 154.27, 190.49.
(neat): 2919, 2869, 1755, 1454, 1165, 1094, 738, 698 cm .
1
Benzo[b]thiophen-2-carbaldehyde: oil. IR (neat): 1665,
1
CDCl ): δ = 7.38 (t, J = 7.6 Hz, 1 H), 7.44 (t, J = 7.6 Hz, 1
H NMR (400 MHz, CDCl ): δ = 3.64–3.75 (m, 2 H), 3.88–
3
–
1 1
515, 1133, 747, 725, 657 cm . H NMR (400 MHz,
3.98 (m, 2 H), 4.12 (d, J = 6.1 Hz, 1 H), 4.43–4.76 (m, 8 H),
13
4.98 (d, J = 11.3 Hz, 1 H), 7.15–7.41 (m, 20 H). C NMR
3
H), 7.81 (d, J = 8.2 Hz, 1 H), 7.86 (d, J = 7.7 Hz, 1 H), 7.92
(100 MHz, CDCl ): δ = 68.21, 73.52, 73.69 (2 × C), 73.91,
3
1
3
(
s, 1 H), 10.03 (s, 1 H). C NMR (100 MHz, CDCl ): δ =
76.01, 78.12, 80.92, 127.79 (3 × C), 127.91, 127.96 (3 × C),
128.08, 128.37, 128.41 (2 × C), 128.45, 136.90, 137.46 (2 ×
C), 137.55, 169.31. HRMS (ESI): m/z [M + H] calcd for
C H O : 539.2428; found: 539.2423.
3
1
1
22.92, 124.96, 126.01, 127.89, 134.36, 138.21, 142.23,
42.93, 184.44.
Propiophenone: oil (commercial, oil). IR (neat): 1686
3
4
35
6
–
1 1
cm . H NMR (400 MHz, CDCl ): δ = 1.23 (t, J = 7.3 Hz, 3
3
©
Georg Thieme Verlag Stuttgart · New York
Synlett 2013, 24, 1707–1711

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