Subscribe to RSS
DOI: 10.1055/s-2006-933102
First Total Synthesis and Assignment of the Absolute Configuration of the Neuronal Cell Protecting Alkaloid Carbazomadurin B
Publication History
Publication Date:
20 February 2006 (online)
Abstract
Using a palladium-catalyzed approach, the first enantioselective synthesis of the neuronal cell protecting agent carbazomadurin B is described and its absolute configuration is assigned.
Key words
alkaloids - aminations - cross-coupling - cyclizations - palladium
- For reviews, see:
-
2a
Chakraborty DP.Roy S. In Progress in the Chemistry of Organic Natural Products Vol. 57:Herz W.Grisebach H.Kirby GW.Steglich W.Tamm C. Springer; Wien: 1991. p.71 -
2b
Chakraborty DP. In The Alkaloids Vol. 44:Cordell GA. Academic Press; New York: 1993. p.257 -
2c
Knölker H.-J.Reddy KR. Chem. Rev. 2002, 102: 4303 -
2d
Fröhner W.Krahl MP.Reddy KR.Knölker H.-J. Heterocycles 2004, 63: 2393 -
2e
Knölker H.-J. Top. Curr. Chem. 2005, 244: 115 - For recent synthetic approaches from other groups, see:
-
3a
Aygün A.Pindur U. J. Heterocycl. Chem. 2003, 40: 411 -
3b
Scott TL.Söderberg BCG. Tetrahedron 2003, 59: 6323 -
3c
Rawat M.Wulff WD. Org. Lett. 2004, 6: 329 -
3d
Crich D.Rumthao S. Tetrahedron 2004, 60: 1513 -
3e
Benavides A.Peralta J.Delgado F.Tamariz J. Synthesis 2004, 2499 -
3f
Duval E.Cuny GD. Tetrahedron Lett. 2004, 45: 5411 -
3g
Kuwahara A.Nakano K.Nozaki K. J. Org. Chem. 2005, 70: 413 -
3h
Pelly SC.Parkinson CJ.van Otterlo WAL.de Koning CB. J. Org. Chem. 2005, 70: 10474 -
3i
Fürstner A.Domostoj MM.Scheiper B. J. Am. Chem. Soc. 2005, 127: 11620 - For recent synthetic approaches from our group, see:
-
4a
Knölker H.-J.Fröhner W.Reddy KR. Eur. J. Org. Chem. 2003, 740 -
4b
Knölker H.-J.Reddy KR. Heterocycles 2003, 60: 1049 -
4c
Knölker H.-J.Knöll J. Chem. Commun. 2003, 1170 -
4d
Knölker H.-J.Wolpert M. Tetrahedron 2003, 59: 5317 -
4e
Knölker H.-J.Krahl MP. Synlett 2004, 528 -
4f
Knölker H.-J.Fröhner W.Heinrich R. Synlett 2004, 2705 -
4g
Kataeva O.Krahl MP.Knölker H.-J. Org. Biomol. Chem. 2005, 3: 3099 -
4h
Czerwonka R.Reddy KR.Baum E.Knölker H.-J. Chem. Commun. 2006, 711 - 5
Kotada N.Shinya K.Furihata K.Hayakawa Y.Seto H. J. Antibiot. 1997, 50: 770 - 6
Lardicci L.Botteghi C.Benedetti E. J. Org. Chem. 1966, 31: 1534 - 8
Dale JA.Mosher HS. J. Am. Chem. Soc. 1973, 95: 512 - 9
Reichardt C.Wilk M. Liebigs Ann. Chem. 1990, 189 - 10
Mori K. Tetrahedron 1974, 30: 3817 - 11
Dehmlow EV.Lissel M. Liebigs Ann. Chem. 1980, 1 -
12a
Van Horn DE.Negishi E. J. Am. Chem. Soc. 1978, 100: 2252 -
12b
Negishi E.Van Horn DE.King AO.Okukado N. Synthesis 1979, 501 -
12c
Rand CL.Van Horn DE.Moore MW.Negishi E. J. Org. Chem. 1981, 46: 4097 -
12d
Negishi E.Van Horn DE.Yoshida T. J. Am. Chem. Soc. 1985, 107: 6639 -
13a
Wolfe JP.Buchwald SL. J. Org. Chem. 1997, 62: 1264 -
13b
Louie J.Driver MS.Hamann BC.Hartwig JF. J. Org. Chem. 1997, 62: 1268 -
13c
Åhman J.Buchwald SL. Tetrahedron Lett. 1997, 38: 6363 -
13d
Hartwig JF. Angew. Chem. Int. Ed. 1998, 37: 2046 ; Angew. Chem. 1998, 110, 2154 -
13e
Muci AR.Buchwald SL. Top. Curr. Chem. 2002, 219: 131 -
14a
Åkermark B.Eberson L.Jonsson E.Pettersson E. J. Org. Chem. 1975, 40: 1365 -
14b
Miller RB.Moock T. Tetrahedron Lett. 1980, 21: 3319 -
14c
Ames DE.Opalko A. Tetrahedron 1984, 40: 1919 -
14d
Furukawa H.Ito C.Yogo M.Wu T.-S. Chem. Pharm. Bull. 1986, 34: 2672 -
14e
Hall RJ.Marchant J.Oliveira-Campos AMF.Queiroz M.-JRP.Shannon PVR. J. Chem. Soc., Perkin Trans. 1 1992, 3439 -
14f
Knölker H.-J.O’Sullivan N. Tetrahedron Lett. 1994, 35: 1695 -
15a
Knölker H.-J.O’Sullivan N. Tetrahedron 1994, 50: 10893 -
15b
Åkermark B.Oslob JD.Heuschert U. Tetrahedron Lett. 1995, 36: 1325 -
15c
Knölker H.-J.Fröhner W. J. Chem. Soc., Perkin Trans. 1 1998, 173 -
15d
Knölker H.-J.Reddy KR.Wagner A. Tetrahedron Lett. 1998, 39: 8267 -
15e
Knölker H.-J.Fröhner W.Reddy KR. Synthesis 2002, 557 -
16a
Hanessian S.Lavalee P. Can. J. Chem. 1975, 53: 2975 -
16b
Hanessian S.Lavalee P. Can. J. Chem. 1977, 55: 562 -
17a
Stille JK. Angew. Chem., Int. Ed. Engl. 1986, 25: 508 ; Angew. Chem. 1986, 98, 483 -
17b
McKean DR.Parrinello G.Renaldo AF.Stille JK. J. Org. Chem. 1987, 52: 422 -
17c
Kalivretenos A.Stille JK.Hegedus LS. J. Org. Chem. 1991, 56: 2883 -
17d
Mitchell TN. Synthesis 1992, 803
References and Notes
Transition Metal Complexes in Organic Synthesis, Part 78. For part 77, see ref. 4h.
7(S)-(-)-2-Methyl-1-butanol (99% purity) from Aldrich.
18Carbazomadurin B (1b): light-yellow crystals, mp 165 °C (dec.). [α]D 24 +13.0 (c 0.05, MeOH); [α]D 19 +16.8 (c 0.37, MeOH). UV (MeOH): λ = 237, 249 (sh), 289 (sh), 299, 347, 356 nm. UV (MeOH, NaOH): λ = 236, 257, 303, 363 nm. IR (KBr): ν = 3477, 3431, 2959, 2929, 2873, 1618, 1584, 1524, 1426, 1377, 1269, 1168, 1075, 972, 819 cm-1. 1H NMR (500 MHz, acetone-d 6): δ = 0.94 (t, J = 7.3 Hz, 3 H), 0.99 (dd, J = 6.3, 5.4 Hz, 3 H), 1.22-1.28 (m, 1 H), 1.42-1.53 (m, 3 H), 1.57 (d, J = 1.1 Hz, 3 H), 1.67-1.73 (m, 1 H), 2.27 (s, 3 H), 2.30-2.42 (m, 2 H), 3.93 (br s, 1 H), 5.02 (s, 2 H), 6.44 (s, 1 H), 6.73 (d, J = 7.7 Hz, 1 H), 6.92 (d, J = 7.7 Hz, 1 H), 7.60 (s, 1 H), 7.79 (br s, 1 H), 8.40 (br s, 1 H), 8.87 (br s, 1 H). 13C NMR and DEPT (125 MHz, acetone-d 6): δ = 11.36 (CH3), 13.22 (CH3), 17.65 (CH3), 19.11 (CH3), 29.70 (CH2), 34.65 (CH), 35.30 (CH2), 37.14 (CH2), 63.49 (CH2), 106.70 (CH), 109.34 (CH), 118.61 (CH), 120.12 (CH), 121.14 (C), 122.08 (C), 122.14 (C), 123.29 (C), 128.13 (C), 130.21 (C), 133.37 (C), 142.47 (C), 142.62 (C), 149.63 (C). MS (EI): m/z (%) = 367 (73) [M+], 366 (10), 365 (27), 351 (100), 349 (11). HRMS: m/z calcd for C23H29NO3 [M+]: 367.2147; found: 367.2157. Anal. Calcd for C23H29NO3: C, 75.17; H, 7.95; N, 3.81. Found: C, 75.12; H, 7.99; N, 3.57.