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DOI: 10.1055/s-0029-1219337
Expedient Route to an Amine Precursor of Halichlorine and Pinnaic Acid from Nitrocyclopent-1-ene
Publikationsverlauf
Publikationsdatum:
19. Januar 2010 (online)
Abstract
Diastereoselective addition of n-propanal to nitrocyclopent-1-ene, aldehyde protection, 1,6-conjugate addition, and cross metathesis provides a facile route to key amine precursors of halichlorine and pinnaic acid.
Key words
nitroalkene - organocatalysis - conjugate addition - alkene metathesis
- Supporting Information for this article is available online:
- Supporting Information
-
1a
Trauner D.Schwarz JB.Danishefsky SJ. Angew. Chem. Int. Ed. 1999, 38: 3542 -
1b
Carson MW.Kim G.Danishefsky SJ. Angew. Chem. Int. Ed. 2001, 40: 4453 -
1c
Christie HS.Heathcock CH. Proc. Natl. Acad. Sci. U.S.A. 2004, 101: 12079 - 2
Clive DLJ.Yu ML.Wang J.Yeh VSC.Kang SZ. Chem. Rev. 2005, 105: 4483 -
3a
Xu S.Arimoto H.Uemura D. Angew. Chem. Int. Ed. 2007, 46: 5746 -
3b
Wu H.Zhang HG.Zhao G. Tetrahedron 2007, 63: 6454 -
3c
Liu DZ.Acharya HP.Yu ML.Wang J.Yeh VSC.Kang SZ.Chiruta C.Jachak SM.Clive DLJ. J. Org. Chem. 2009, 74: 7417 -
4a
Kim H.Seo JH.Shin KJ.Kim DJ.Kim D. Heterocycles 2006, 70: 143 -
4b
Caprio V. Synlett 2007, 1219 -
4c
Clive DLJ.Li ZY.Yu ML. J. Org. Chem. 2007, 72: 5608 -
4d
Hurley PB.Dake GR. J. Org. Chem. 2008, 73: 4131 -
4e
Keck GE.Heumann SA. Org. Lett. 2008, 10: 4783 -
4f
Wang LH.Prabhudas B.Clive DLJ. J. Am. Chem. Soc. 2009, 131: 6003 -
4g
Yamamoto Y.Yasuda Y.Nasu H.Tomioka K. Org. Lett. 2009, 11: 2007 -
4h
Yang SH.Clark GR.Caprio V. Org. Biomol. Chem. 2009, 7: 2981 -
4i
Amordea SM.Jewetta IT.Martin SF. Tetrahedron 2009, 65: 3222 - 5
Andrey O.Vidonne A.Alexakis A. Tetrahedron Lett. 2003, 44: 7901 -
6a
Risaliti A.Forchiassin M.Valentin E. Tetrahedron 1968, 24: 1889 -
6b
Chinchilla R.Bäckvall JE. Tetrahedron Lett. 1992, 33: 5641 -
6c
Denmark SE.Thorarensen A. Chem. Rev. 1996, 96: 137 -
6d
Diez D.Gil MJ.Moro RF.Marcos IS.Garcia P.Basabe P.Garrido NM.Broughton HB.Urones JG. Tetrahedron 2007, 63: 740 -
6e
Domingo LR.Picher MT.Arroyo P. Eur. J. Org. Chem. 2006, 2570 - 7
Corey EJ.Estreicher H. J. Am. Chem. Soc. 1978, 100: 6294 - 10
Maki K.Kania M.Shibasaki M. Tetrahedron 2007, 63: 4250 - 11
Wade PA.Morrow S.Hardinger S. J. Org. Chem. 1982, 47: 365 - 12
Bernardi L.Cantarero-Lopez J.Jesus B.Jørgensen KA. J. Am. Chem. Soc. 2007, 129: 5772 - 13
Garber SB.Kingsbury JS.Gray BL.Hoveyda AH. J. Am. Chem. Soc. 2000, 122: 8168
References and Notes
Cambridge Crystallographic Data Centre deposition numbers: 6a: 753693; 6b: 753694.
9Schemes reflect the stereochemical orientation in the crystal structures for convenience of the reader. In fact, the opposite absolute stereochemistry is required for 1 and 2.
14
Data for Selected
CompoundEthyl (
E
)-5-{2-[1-(1,3-dioxan-2-yl)ethyl]-1-nitrocyclo-pentyl}pent-3-enoate (11)
(2E)-Ethyl-2,4-pentadienoate
(0.50 g, 4.0 mmol) was added to of 2-[1-(2-nitrocyclopentyl)ethyl]-1,3-dioxane
(5a, 0.83 g, 3.6 mmol), Cs2CO3 (1.33
g, 3.6 mmol), TBAI (0.06 g, 5 mol%) in xylene (70 mL) and
CHCl3 (10 mL) and stirred at r.t. for 16 h. Water (100
mL) was added and the mixture extracted with EtOAc (3 × 60
mL). The organic layers were washed with brine (100 mL), dried (MgSO4),
filtered, and concentrated. The crude material was purified by silica
gel chromatography using PE-EtOAc (95:5) as eluent to give the
ester 11 as a colourless oil (1.13 g, 88%).
IR (CHCl3): ν = 2976,
1729, 1531, 1470, 1428, 1372, 1280, 1155 cm-¹. ¹H
NMR (400 MHz, CDCl3): δ = 5.72
(1 H, dt, J = 15.4, 6.8 Hz CH=CHCH2CO2Et), 5.50
(1 H, ddd, J = 15.4, 7.6, 6.8
Hz, CH=CHCH2CO2Et),
4.38 (1 H, d, J = 4.0 Hz, CHO2),
4.15 (2 H, q, J = 7.2 Hz, CH
2CH3), 4.14-4.08 [2
H, m, (OCH
a
Hb)2],
3.79-3.70 [2 H, m, (OCHa
H
b)2],
3.12 (1 H, dd, J = 14.4, 6.8
Hz, CCH
a
HbCH=CH),
3.05 (2 H, d, J = 6.8 Hz, CH2CO2Et),
2.52-2.44 (1 H, m, CHCNO2), 2.38 (1 H, dd,
J = 14.4, 7.6 Hz, CCH
a
H
b
CH=CH), 2.32-2.65 [1
H, m, CCH
aHbCH2)2],
2.10-1.58 [7 H, m, CHCH(CH
2)2CHa
H
bCNO2,
(OCH2)CH
aHb],
1.36-1.31 [1 H, m, (OCH2)CHa
H
b], 1.27 (3 H, t, J = 7.2 Hz, CH2CH
3), 0.73 (3 H, d, J = 7.2 Hz, CHCH
3) ppm.
(100 MHz, CDCl3): δ = 171.6,
128.0, 127.3, 104.3, 99.4, 66.9, 66.8, 60.7, 49.2, 40.0, 38.1, 35.9,
35.1, 26.6, 25.8, 22.2, 14.2, 10.8 ppm. HRMS: m/z calcd
for C18H30NO6: 356.2068; found:
356.2062 [M + H]+.
Anal. Calcd for C18H29NO6: C, 60.80;
H, 8.17; N, 3.94. Found: C, 61.10; H, 8.28; N, 3.69.
Data for Selected Compound tert -Butyl ( E )-4-{1-amino-2-[1-(1,3-dioxan-2-yl)ethyl]-cyclopentyl}but-2-enoate (14) Methyl (E)-4-{2-[1-(1,3-dioxan-2-yl)ethyl]-1-nitrocyclopentyl}but-2-enoate (12, 0.05 g, 0.14 mmol), Zn dust (0.18 g, 2.71 mmol), and HCl (1 M, 1.30 mL, 1.35 mmol) was stirred in i-PrOH (2 mL) overnight at r.t. 1 M KOH was added to the reaction until pH >11, then extracted with EtOAc (4 × 10 mL). The organic layers were dried (Na2SO4), filtered, and concentrated to yield amine 14 as a clear oil (0.04 g, 80%). IR (CHCl3): ν = 3010, 2976, 1704, 1449, 1392, 1369, 1240, 1154 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 6.96 [1 H, ddd, J = 15.6, 8.4, 7.2 Hz, CH=CHCO2(CH 3)3], 5.86 [1 H, dt, J = 15.6, 1.2 Hz, CH=CHCO2(CH 3)3], 4.43 (1 H, d, J = 3.6 Hz, CHO2), 4.16-4.11 [2 H, m, (OCH a Hb)2], 3.79-3.72 [2 H, m, (OCHa H b)2], 2.50 (1 H, ddd, J = 13.6, 8.4, 1.2 Hz, CH a HbCH=CH), 2.32 (1 H, ddd, J = 13.6, 7.2, 1.2 Hz, CHa H b CH=CH), 2.13-2.00 [1 H, m, (OCH2)CH aHb], 1.87-1.35 [18 H, m, CHCH(CH 2)3, (OCH2)CHa H b, CO2(CH 3)3], 0.99 (3 H, d, J = 7.2, CHCH 3) ppm. ¹³C NMR (100 MHz, CDCl3): δ = 165.9, 144.9, 125.7, 105.3, 80.1, 67.0, 66.9, 62.0, 47.6, 44.9, 40.3, 37.0, 28.2, 27.8, 25.9, 22.5, 13.5 ppm. HRMS: m/z calcd for C19H34NO4: 340.2482; found: 340.2492 [M + H]+; m/z calcd for C19H34NO4Na: 362.2302; found: 362.2303 [M + Na]+.