D
Synlett
S. Chiha et al.
Letter
(
3) Liebau, G.; Riegger, A. J.G.; Schanzenbächer, P.; Steilner, H.;
(20) Detailed experimental procedures and characterization data are
given in the Supporting Information.
Oehrlein, S. Br. J. Clin. Pharmacol. 1982, 14, 193S.
(
(
4) Song, J. C.; White, C. M. Clin. Pharmacokinet. 2002, 41, 207.
5) Cendrowska, I.; Bańkowski, K.; Iskra-Jopa, J. Acta. Pol. Pharm.
Synthesis of Di-tert-butyl-(2S,4R)-4,5-diallylpyrrolidine-1,2-
dicarboxylate (8)
2
003, 60, 141.
6) Urbach, H.; Henning, R.; Teetz, V.; Geiger, R.; Becker, R.; Gaul, H.
Hoechst AG) DE 3151690, 1981.
7) (a) Shen, J.; Liu, D.; An, Q.; Liu, Y.; Zhang, W. Adv. Synth. Catal.
012, 354, 3311. (b) Kankan, R. N.; Rao, D. R.; Phull, M. S.;
To a solution of 0.55 g (1.61 mmol, 1.0 equiv) of methoxyproline
(12) in 13 ml CH Cl were added 0.64 ml (4.03 mmol, 2.5 equiv)
(
(
2
2
(
of allyl-TMS at –78 °C. Afterwards, 0.85 ml (3.22 mmol, 2 equiv)
of BF ·OEt (48%) were added dropwise over 5 min. After 2 h of
3
2
2
stirring at –78 °C, the reaction mixture was quenched with 5 ml
of a saturated solution of NaHCO3 and the aqueous layer
extracted three times with 30 ml of MTBE. The combined
organic layers were washed two times with a saturated solution
Sawant, A.; Birari, D. R. US7973173B2, 2011. (c) Brion, F.; Marie,
C.; Mackiewicz, P.; Roul, J. M.; Buendia, J. Tetrahedron Lett. 1992,
33, 4889. (d) Henning, R.; Urbach, H. Tetrahedron Lett. 1983, 24,
5343.
of sodium chloride, dried over MgSO , filtered, and evaporated
4
(
8) (a) Ogba, O. M.; Warner, N. C.; O’Leary, D. J.; Grubbs, R. H. Chem.
Soc. Rev. 2018, 47, 4510. (b) Grubbs, R. H. Handbook of Metathe-
sis; Wiley-VCH: Weinheim, 2003.
to dryness. After chromatographic separation of the diastereo-
meric mixture (17:1 ‘cis/trans’) and purification on silica
(EtOAc/CyHex = 1:4) 0.42 g (1.19 mmol, 74%) of the diallylated
1
(9) Chiha, S.; Soicke, A.; Barone, M.; Müller, M.; Bruns, J.; Opitz, R.;
Neudörfl, J.-M.; Kühne, R.; Schmalz, H.-G. Eur. J. Org. Chem.
proline 8 was obtained as a colorless oil. H NMR (300 MHz,
CDCl , mixture of rotamers): = 5.76–5.50 (m, 2 H, H-10/13),
3
2
018, 455.
4.99–4.85 (m, 4 H, H-11/14), 4.10–3.93 (m, 1 H, H-2), 3.58–3.42
(m, 1 H, H-5), 2.56–2.40 (m, 1 H, H-4), 2.19–1.72 (m, 6 H, H-
3/9/12), 1.34;1.31 (2 × s, 18 H, H-8) ppm. C NMR (75 MHz,
(
10) Zaminer, J.; Brockmann, C.; Huy, P.; Opitz, R.; Reuter, C.;
Beyermann, M.; Freund, C.; Müller, M.; Oschkinat, H.; Kühne, R.;
Schmalz, H.-G. Angew. Chem. Int. Ed. 2010, 49, 7111.
13
CDCl , mixture of rotamers): = 172.2, 172.0 (C-6), 154.1, 153.7
3
(
11) Berndt, M.; Hölemann, A.; Niermann, A.; Bentz, C.; Zimmer, R.;
Reissig, H.-U. Eur. J. Org. Chem. 2012, 1299.
(C-15), 136.4, 135.7, 135.4 (C-10/13), 116.8, 116.7 (C-11/14),
80.6 (C-7), 79.6, 79.5 (C-16), 62.9 (C-2), 59.4, 58.9 (C-5), 41.3,
40.2 (C-4), 38.8 (C-12), 38.1, 37.8 (C-9), 33.3, 32.4 (C-3), 28.3,
(12) Aggarwal, V. K.; Astle, C. J.; Iding, H.; Wirz, B.; Rogers-Evans, M.
Tetrahedron Lett. 2005, 46, 945.
+
27.9 (C-8/17) ppm. HRMS (ESI): m/z = [M + Na] calcd: 374.2302;
(
(
13) Hosomi, A.; Sakurai, H. Tetrahedron Lett. 1976, 17, 1295.
14) Hanessian, S.; Margarita, R.; Hall, A.; Johnstone, S.; Tremblay,
M.; Parlanti, L. J. Am. Chem. Soc. 2002, 124, 13342.
found: 374.2301.
Synthesis of Di-tert-butyl-(2S,3aR,7aS)-2,3,3a,4,7,7a-hexa-
hydro-1H-indole-1,2-dicarboxylate (7)
(
15) Voigtritter, K.; Ghorai, S.; Lipshutz, B. H. J. Org. Chem. 2011, 76,
To a solution of 0.40 g (1.14 mmol, 1.00 equiv) of diallylproline
8 in 35 ml CH Cl was added 0.05 g (0.06 mmol, 0.05 equiv)
4697.
2
2
(
16) Belvisi, L.; Colombo, L.; Colombo, M.; Di Giacomo, M.; Manzoni,
L.; Vodopivec, B.; Scolastico, C. Tetrahedron 2001, 57, 6463.
Grubbs II catalyst and 0.02 g (0.09 mmol, 0.08 equiv) CuI at
room temperature. After stirring for 2.5 h, the solution was
evaporated under reduced pressure to dryness. After chromato-
graphic purification on silica (CyHex/EtOAc = 4:1) the hexahy-
(17) Jung, M. E.; Lyster, M. A. J. Chem. Soc., Chem. Commun. 1978, 315.
18) Coste, J.; Le-Nguyen, D.; Castro, B. Tetrahedron Lett. 1990, 31,
(
2
05.
19) CCDC 1862524 (for 2a), CCDC 1896252 (for 1), and CCDC
896253 (for 16) contain the supplementary crystallographic
data for this paper. The data can be obtained free of charge from
The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/getstructures.
droindole 7 (0.35 g, 1.08 mmol, 95%) was obtained as colorless
1
(
oil. H NMR (300 MHz, CDCl ): = 5.72–5.62 (m, 2 H, H-7/8),
3
1
4.37–4.11 (m, 1 H, H-2), 3.25–3.04 (m, 1 H, H-5), 2.32–1.65 (m,
13
7 H, H-3/4/6/9), 1.46 (s, 18 H, H-12/15) ppm. C NMR (75 MHz,
CDCl ): = 172.2 (C-10), 154.3 (C-13), 126.4, 126.1 (C-7/8), 80.8
3
(C-11), 79.6 (C-14), 61.0 (C-2), 60.2 (C-5), 40.0 (C-4), 34.5 (C-9),
3
2.7 (C-6), 30.4 (C-3), 28.4, 28.0 (C-12/15) ppm. HRMS (ESI):
+
m/z = [M + Na] calcd: 346.1989; found: 346.1987.
©
Georg Thieme Verlag Stuttgart · New York — Synlett 2019, 30, A–D