European Journal of Organic Chemistry
10.1002/ejoc.202001397
FULL PAPER
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1
ꢃꢉꢅꢇ
1
7
29 cm . ꢀꢁ = -23.0 (C2H5OH, c = 2.3). H NMR (500.03 MHz, CDCl3,
ꢂ
Acknowledgements
δ): 0.9(18) (d, J = 6.6 Hz, 3H; 17-CH3 or 18-CH3), 0.9(21) (d, J = 6.6 Hz,
3
1
1
1
H; 18-CH3 or 17-CH3), 1.45-1.49 (m, 1H; 16-CH), 1.49-1.55 (m, 1H;
3-CH2), 1.53 (s, 3H; 15-CH3), 1.83-1.92 (m, 2H; 12-CH, 14-CH2),
.93-2.01 (m, 2H; 11-CH2, 13-CH2), 2.06 (dd, J = 12.1, 6.9 Hz, 1H;
1-CH2), 2.33 (ddd, J = 12.8, 9.4, 5.0 Hz, 1H; 14-CH2), 7.31 (ddd,
The authors would like to express their gratitude to the
Collective Use Chemical Service Center of the Siberian Branch
of Russian Academy of Sciences for the obtained spectra and
analytical data, as well as Dr. A.A. Nefedov (N.N. Vorozhtsov
Novosibirsk Institute of Organic Chemistry SB RAS) for the
study of enantiomeric purity of reaction mixtures. All calculations
were carried out on a cluster computer in the regional centre for
shared computer equipment at the Ufa Institute of Chemistry
UFRC RAS. The reported study was funded by RFBR, project
number 19-33-90080.
J = 8.1, 7.1, 1.2 Hz, 1H; 7-CH(Ar)), 7.42 (ddd, J = 8.1, 7.1, 1.2 Hz, 1H;
-CH(Ar)), 7.83 (ddd, J = 8.1, 1.1, 0.6 Hz, 1H; 6-CH(Ar)), 7.98 ppm (ddd,
8
1
3
1
J = 8.1, 1.1, 0.6 Hz, 1H; 9-CH(Ar)). C{ H} NMR (125.74 MHz, CDCl3,
δ): 21.(58) (C-17 or C-18), 21.(61) (C-18 or C-17), 29.0 (C-15), 30.0
(C-13), 33.8 (C-16), 40.7 (C-14), 46.2 (C-11), 46.8 (C-12), 49.2 (C-10),
121.5 (C-6), 122.8 (C-9), 124.5 (C-7), 125.8 (C-8), 135.2 (C-5), 153.4
+
32
+∙
(C-4), 182.3 ppm (C-2). HRMS (ESI ): calculated (C16H21 S1N1)
259.1389; found 259.1391.
Keywords: Benzimidazoles • benzoxazoles • benzothiazoles •
monoterpenoids • single-stage synthesis • norcamphor •
(+)-camphor • (-)-fenchone
2
-((1R,3S)-3-isopropyl-1-methylcyclopentyl)-1H-benzo[d]imidazole
ꢃꢉꢅꢇ
(11a): white powder (5.9 g, 37% yield). ).ꢈ ꢀꢁꢂ = +9.0 (C2H5OH,
c = 0.80); m.p. 198.8-199.7°C. IR: 3051, 2956, 1622, 1531, 1411, 1276,
-
1
1
992, 751 cm . H NMR (500.03 MHz, CDCl3+CD3OD, δ): 0.83 (d,
J = 6.9 Hz, 3H; 17-CH3 or 18-CH3), 0.84 (d, J = 6.9 Hz, 3H; 18-CH3 or
1
3
1
1
8
7-CH3), 1.35-1.38 (m, 1H; 12-CH), 1.40-1.43 (m, 1H; 13-CH2), 1.43 (s,
H; 15-CH3), 1.78-1.86 (m, 3H; 11-CH2, 14-CH2, 16-CH), 1.89-1.96 (m,
H; 13-CH2), 1.97-2.03 (1H, m; 11-CH2), 2.27 (ddd, J = 15.4, 9.8, 5.5 Hz,
H; 14-CH2), 3.66 (br.s, 1H; 1-NH), 7.14-7.16 (m, 2H; 7-CH(Ar),
[1]
I. A. Dvornikova, E. V. Buravlev, I. V. Fedorova, O. G. Shevchenko,
I. Y. Chukicheva, A. V. Kutchin, Russ. Chem. Bull. 2019, 68, 1000–
1
3
1
-CH(Ar)), 7.51-7.53 ppm (m, 2H; 6-CH(Ar), 9-CH(Ar)). C{ H} NMR
1005.
(125.74 MHz, CDCl3, δ): 21.4 (17-C or 18-C), 21.5 (18-C or 17-C), 27.5
[
[
2]
3]
T. H. M. Jonckers, M. C. Rouan, G. Haché, W. Schepens, S.
Hallenberger, J. Baumeister, J. C. Sasaki, Bioorganic Med. Chem.
Lett. 2012, 22, 4998–5002.
(15-C), 29.6 (13-C), 33.8 (12-C), 38.7 (14-C), 44.2 (10-C), 44.5 (11-C),
4
1
2
6.3 (16-C), 114.6 (6-C, 9-C), 122.4 (7-C, 8-C), 137.6 (4-C, 5-C),
62.6 ppm (2-C). HRMS (ESI ): calculated (C16H22N2) 242.1778; found
42.1775.
+
+∙
A. Kamil, S. Jahan, A. Khan, Z. S. Saify, S. Akhtar, M. Iqbal
Choudhary, K. M. Khan, S. Perveen, M. Taha, F. Rahim, Med.
Chem. Res. 2014, 23, 4447–4454.
2-(cyclopentylmethyl)benzo[d]oxazole (13): colourless oil (356 mg,
-
1
65% yield). IR: 3057, 2953, 1570, 1456, 1242, 1169, 837, 746 cm .
ꢋꢌꢅꢍ
1
[4]
[5]
G. Yadav, S. Ganguly, Eur. J. Med. Chem. 2015, 97, 419–443.
A. S. Latysheva, V. A. Zolottsev, A. V. Veselovsky, K. A.
Scherbakov, G. E. Morozevich, V. S. Pokrovsky, R. A. Novikov, V.
P. Timofeev, Y. V. Tkachev, A. Y. Misharin, Steroids 2020, 153,
ꢀ
ꢁꢊ = +30.4 (CHCl3, c = 1.17).
H NMR (500.13 MHz, CDCl3, δ):
1
1
2
7
1
.27-1.34 (m, 2H; 12-CH2, 15-CH2), 1.53-1.61 (m, 2H; 13-CH2, 14-CH2),
.63-1.71 (m, 2H; 13-CH2, 14-CH2), 1.83-1.89 (m, 2H; 12-CH2, 15-CH2),
.47 (hept, J = 7.7 Hz, 1H; 11-CH), 2.93 (d, J = 7.5 Hz, 2H; H-10),
.26-7.29 (m, 2H; H-7, H-8), 7.44-7.48 (m, 1H; H-6), 7.64-7.67 ppm (m,
108534.
1
3
1
H; H-9). C{ H} NMR (125.74 MHz, CDCl3, δ): 25.1 (C-13, C-14), 32.6
[
6]
H. J. M. Gijsen, M. A. J. De Cleyn, M. Surkyn, G. R. E. Van
Lommen, B. M. P. Verbist, M. J. M. A. Nijsen, T. Meert, J. Van
Wauwe, J. Aerssens, Bioorganic Med. Chem. Lett. 2012, 22, 547–
(
(
(
C-12, C-15), 34.6 (C-10), 38.3 (C-11), 110.4 (C-6), 119.7 (C-9), 124.1
C-8), 124.5 (C-7), 141.6 (C-4), 150.9 (C-5), 167.1 ppm (C-2). HRMS
ESI ): calculated (C13H15O1N1) 201.1148; found 201.1149.
+
+∙
552.
2
-(cyclopentylmethyl)benzo[d]thiazole (14): colourless oil (355 mg,
[
[
7]
8]
L. Racane, R. Stojkovic, V. Tralic-Kulenovic, G. Karminski-Zamola,
Molecules 2006, 11, 325–333.
-
1
60% yield). IR: 3063, 2951, 1518, 1437, 1311, 1244, 1105, 758 cm .
ꢃꢎꢅꢎ
ꢂ
1
ꢀ
ꢁ
= +27.6 (CHCl3, c = 1.04). H NMR (500.03 MHz, CDCl3, δ):
.28-1.35 (m, 2H; H-12, H-15), 1.53-1.61 (m, 2H; H-13, H-14), 1.64-1.70
m, 2H; H-13, H-14), 1.82-1.88 (m, 2H; H-12, H-15), 2.39 (hept,
J = 7.6 Hz, 1H; H-11), 3.10 (d, J = 7.5 Hz, 2H; H-10), 7.33 (ddd, J = 8.4,
.1, 1.2 Hz, 1H; H-7), 7.43 (ddd, J = 8.4, 7.1, 1.2 Hz, 1H; H-8), 7.82 (ddd,
J = 8.1, 1.1, 0.6 Hz, 1H; H-6), 7.96 ppm (ddd, J = 8.1, 1.1, 0.6 Hz, 1H;
N. S.K. Mohanty, A. Khuntia, H. Yellasubbaiah, C. Ayyanna, B.N.
Sudha, Beni-Suef Univ. J. Basic Appl. Sci. 2018, 7, 646–651.
P. N. Kishore Babu, B. Ramadevi, Y. Poornachandra, C. Ganesh
Kumar, Med. Chem. Res. 2014, 23, 3970–3978.
1
(
[9]
7
[
10]
R. S. Keri, M. R. Patil, S. A. Patil, S. Budagupi, Eur. J. Med. Chem.
1
3
1
H-6). C{ H} NMR (125.74 MHz, CDCl3, δ): 25.2 (C-13, C-14), 32.7
2015, 89, 207–251.
(
(
(
C-12, C-15), 40.5 (C-10), 40.7 (C-11), 121.6 (C-6), 122.7 (C-9), 124.7
C-7), 125.9 (C-8), 135.4 (C-5), 153.4 (C-4), 171.9 ppm (C-2). HRMS
ESI ): calculated (C13H15 S1N1) 217.0920; found 217.0923.
[11]
V. R. Mishra, C. W. Ghanavatkar, S. I. Qureshi, Comput. Biol.
Chem. 2019, 78, 330–337.
+
32
+∙
[
[
12]
13]
H. Z. Zhang, Z. L. Zhao, C. H. Zhou, Eur. J. Med. Chem. 2018, 144,
2
-(cyclopentylmethyl)-1H-benzo[d]imidazole (15): white powder
444–492.
ꢃꢄꢅꢇ
(273 mg,
50%
yield).ꢈ ꢀꢁꢂ = +24.6
(CHCl3,
c = 1.30);
A. M. Bernard, M. G. Cabiddu, S. De Montis, R. Mura, R. Pompei,
Bioorganic Med. Chem. 2014, 22, 4061–4066.
m.p. 213.3-214.4°C. IR: 3084, 2945, 2864, 2683, 1624, 1541, 1435,
-1
1
1
2
275, 1030, 743 cm . H NMR (500.03 MHz, CDCl3, δ): 1.22–1.30 (m,
H; H-12, H-15), 1.47-1.54 (m, 2H; H-13, H-14), 1.56-1.63 (m, 2H; H-13,
[14]
J. Neyts, E. De Clercq, R. Singha, Y. H. Chang, A. R. Das, S. K.
Chakraborty, S. C. Hong, S. C. Tsay, M. H. Hsu, J. R. Hwu, J. Med.
Chem. 2009, 52, 1486–1490.
H-14), 1.75-1.81 (m, 2H; H-12, H-15), 2.43 (hept, J = 7.8 Hz, 1H; H-11),
2.95 (d, J = 7.6 Hz, 2H; H-10), 7.19-7.22 (m, 2H; H-7, H-8), 7.52-7.56 (m,
1
3
1
2H; H-6, H-9), 11.55 ppm (br.s., 1H; H-1). C{ H} NMR (125.74 MHz,
[
[
15]
16]
R. N. Brown, R. Cameron, D. K. Chalmers, S. Hamilton, A. Luttick,
G. Y. Krippner, D. B. McConnell, R. Nearn, P. C. Stanislawski, S. P.
Tucker, et al., Bioorganic Med. Chem. Lett. 2005, 15, 2051–2055.
M. J. Tebbe, W. A. Spitzer, F. Victor, S. C. Miller, C. C. Lee, T. R.
CDCl3, δ): 25.1 (C-13, C-14), 32.8 (C-12, C-15), 35.5 (C-10), 39.5 (C-11),
14.8 (C-6, C-9), 122.2 (C-7, C-8), 138.7 (C-4, C-5), 155.1 ppm (C-2).
1
+
+∙
HRMS (ESI ): calculated (C13H16N2) 200.1308; found 200.1310.
1
1
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