First Total Synthesis and Assignment of the Absolute Configuration of the Neuronal Cell Protecting Alkaloid Carbazomadurin B

Jan Knöll; Hans-Joachim Knölker

doi:10.1055/s-2006-933102

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Synlett 2006(4): 0651-0653
DOI: 10.1055/s-2006-933102

LETTER

First Total Synthesis and Assignment of the Absolute Configuration of the Neuronal Cell Protecting Alkaloid Carbazomadurin B

Jan Knöll, Hans-Joachim Knölker*
Department Chemie, Technische Universität Dresden, Bergstraße 66, 01069 Dresden, Germany
Fax: +49(351)46337030; e-Mail: hans-joachim.knoelker@tu-dresden.de;

Further Information

Publication History

Received 16 December 2005
Publication Date:
20 February 2006 (online)

Abstract
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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

References and Notes

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

Google Scholar
2b Chakraborty DP. In The Alkaloids Vol. 44: Cordell GA. Academic Press; New York: 1993. p.257

Google Scholar
2c Knölker H.-J. Reddy KR. Chem. Rev. 2002, 102: 4303

Google Scholar
2d Fröhner W. Krahl MP. Reddy KR. Knölker H.-J. Heterocycles 2004, 63: 2393

Google Scholar
2e Knölker H.-J. Top. Curr. Chem. 2005, 244: 115

Google Scholar
For recent synthetic approaches from other groups, see:
3a Aygün A. Pindur U. J. Heterocycl. Chem. 2003, 40: 411

Crossref Google Scholar
3b Scott TL. Söderberg BCG. Tetrahedron 2003, 59: 6323

Crossref Google Scholar
3c Rawat M. Wulff WD. Org. Lett. 2004, 6: 329

Crossref Google Scholar
3d Crich D. Rumthao S. Tetrahedron 2004, 60: 1513

Crossref Google Scholar
3e Benavides A. Peralta J. Delgado F. Tamariz J. Synthesis 2004, 2499

Crossref Google Scholar
3f Duval E. Cuny GD. Tetrahedron Lett. 2004, 45: 5411

Crossref Google Scholar
3g Kuwahara A. Nakano K. Nozaki K. J. Org. Chem. 2005, 70: 413

Crossref Google Scholar
3h Pelly SC. Parkinson CJ. van Otterlo WAL. de Koning CB. J. Org. Chem. 2005, 70: 10474

Crossref Google Scholar
3i Fürstner A. Domostoj MM. Scheiper B. J. Am. Chem. Soc. 2005, 127: 11620

Crossref Google Scholar
For recent synthetic approaches from our group, see:
4a Knölker H.-J. Fröhner W. Reddy KR. Eur. J. Org. Chem. 2003, 740

Crossref Google Scholar
4b Knölker H.-J. Reddy KR. Heterocycles 2003, 60: 1049

Crossref Google Scholar
4c Knölker H.-J. Knöll J. Chem. Commun. 2003, 1170

Crossref Google Scholar
4d Knölker H.-J. Wolpert M. Tetrahedron 2003, 59: 5317

Crossref Google Scholar
4e Knölker H.-J. Krahl MP. Synlett 2004, 528

Crossref Google Scholar
4f Knölker H.-J. Fröhner W. Heinrich R. Synlett 2004, 2705

Crossref Google Scholar
4g Kataeva O. Krahl MP. Knölker H.-J. Org. Biomol. Chem. 2005, 3: 3099

Crossref Google Scholar
4h Czerwonka R. Reddy KR. Baum E. Knölker H.-J. Chem. Commun. 2006, 711

Crossref Google Scholar
5 Kotada N. Shinya K. Furihata K. Hayakawa Y. Seto H. J. Antibiot. 1997, 50: 770

Google Scholar
6 Lardicci L. Botteghi C. Benedetti E. J. Org. Chem. 1966, 31: 1534

Google Scholar
8 Dale JA. Mosher HS. J. Am. Chem. Soc. 1973, 95: 512

Crossref Google Scholar
9 Reichardt C. Wilk M. Liebigs Ann. Chem. 1990, 189

Google Scholar
10 Mori K. Tetrahedron 1974, 30: 3817

Crossref Google Scholar
11 Dehmlow EV. Lissel M. Liebigs Ann. Chem. 1980, 1

Crossref Google Scholar
12a Van Horn DE. Negishi E. J. Am. Chem. Soc. 1978, 100: 2252

Crossref Google Scholar
12b Negishi E. Van Horn DE. King AO. Okukado N. Synthesis 1979, 501

Crossref Google Scholar
12c Rand CL. Van Horn DE. Moore MW. Negishi E. J. Org. Chem. 1981, 46: 4097

Crossref Google Scholar
12d Negishi E. Van Horn DE. Yoshida T. J. Am. Chem. Soc. 1985, 107: 6639

Crossref Google Scholar
13a Wolfe JP. Buchwald SL. J. Org. Chem. 1997, 62: 1264

Google Scholar
13b Louie J. Driver MS. Hamann BC. Hartwig JF. J. Org. Chem. 1997, 62: 1268

Google Scholar
13c Åhman J. Buchwald SL. Tetrahedron Lett. 1997, 38: 6363

Google Scholar
13d Hartwig JF. Angew. Chem. Int. Ed. 1998, 37: 2046 ; Angew. Chem. 1998, 110, 2154

Google Scholar
13e Muci AR. Buchwald SL. Top. Curr. Chem. 2002, 219: 131

Google Scholar
14a Åkermark B. Eberson L. Jonsson E. Pettersson E. J. Org. Chem. 1975, 40: 1365

Crossref Google Scholar
14b Miller RB. Moock T. Tetrahedron Lett. 1980, 21: 3319

Crossref Google Scholar
14c Ames DE. Opalko A. Tetrahedron 1984, 40: 1919

Crossref Google Scholar
14d Furukawa H. Ito C. Yogo M. Wu T.-S. Chem. Pharm. Bull. 1986, 34: 2672

Crossref Google Scholar
14e Hall RJ. Marchant J. Oliveira-Campos AMF. Queiroz M.-JRP. Shannon PVR. J. Chem. Soc., Perkin Trans. 1 1992, 3439

Crossref Google Scholar
14f Knölker H.-J. O’Sullivan N. Tetrahedron Lett. 1994, 35: 1695

Crossref Google Scholar
15a Knölker H.-J. O’Sullivan N. Tetrahedron 1994, 50: 10893

Article in Thieme Connect Google Scholar
15b Åkermark B. Oslob JD. Heuschert U. Tetrahedron Lett. 1995, 36: 1325

Article in Thieme Connect Google Scholar
15c Knölker H.-J. Fröhner W. J. Chem. Soc., Perkin Trans. 1 1998, 173

Article in Thieme Connect Google Scholar
15d Knölker H.-J. Reddy KR. Wagner A. Tetrahedron Lett. 1998, 39: 8267

Article in Thieme Connect Google Scholar
15e Knölker H.-J. Fröhner W. Reddy KR. Synthesis 2002, 557

Article in Thieme Connect Google Scholar
16a Hanessian S. Lavalee P. Can. J. Chem. 1975, 53: 2975

Google Scholar
16b Hanessian S. Lavalee P. Can. J. Chem. 1977, 55: 562

Google Scholar
17a Stille JK. Angew. Chem., Int. Ed. Engl. 1986, 25: 508 ; Angew. Chem. 1986, 98, 483

Article in Thieme Connect Google Scholar
17b McKean DR. Parrinello G. Renaldo AF. Stille JK. J. Org. Chem. 1987, 52: 422

Article in Thieme Connect Google Scholar
17c Kalivretenos A. Stille JK. Hegedus LS. J. Org. Chem. 1991, 56: 2883

Article in Thieme Connect Google Scholar
17d Mitchell TN. Synthesis 1992, 803

Article in Thieme Connect Google Scholar

1

Transition Metal Complexes in Organic Synthesis, Part 78. For part 77, see ref. 4h.

7

(S)-(-)-2-Methyl-1-butanol (99% purity) from Aldrich.

18

Carbazomadurin 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.