Enantioselective Synthesis of the C1-C15 Fragment of Dolabelide C

Aurélie Vincent; Joëlle Prunet

doi:10.1055/s-2006-949614

Subscribe to RSS

Please copy the URL and add it into your RSS Feed Reader.

https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml

Share / Bookmark

Facebook X Linkedin Weibo

Download PDF

Synlett 2006(14): 2269-2271
DOI: 10.1055/s-2006-949614

LETTER

Enantioselective Synthesis of the C1-C15 Fragment of Dolabelide C

Aurélie Vincent, Joëlle Prunet*
Laboratoire de Synthèse Organique, UMR CNRS 7652, Ecole Polytechnique, DCSO, 91128 Palaiseau, France
Fax: +33(1)69333851; e-Mail: joelle.prunet@polytechnique.fr;

Further Information

Publication History

Received 18 May 2006
Publication Date:
24 August 2006 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

Abstract

A synthesis of the C1-C15 fragment of dolabelide C is reported. The key step is a diastereoselective Mukaiyama aldol reaction to form the C6-C7 bond, followed by reduction and deoxygenation of the carbonyl group at C5. The trisubstituted vinyl iodide is introduced via the corresponding vinyl boronate by cross metathesis.

Key words

stereoselective synthesis - aldol reactions - metathesis - Michael additions - acetals

References and Notes

1 Ojika M. Nagoya T. Yamada K. Tetrahedron Lett. 1995, 36: 7491

Crossref Google Scholar
2 Suenaga K. Nagoya T. Shibata T. Kigoshi H. Yamada K. J. Nat. Prod. 1997, 60: 155

Crossref Google Scholar
3 Ohtani I. Kusumi T. Kashman Y. Kakisawa H. J. Am. Chem. Soc. 1991, 113: 4092

Crossref Google Scholar
4a C16-C24: Grimaud L. de Mesmay R. Prunet J. Org. Lett. 2002, 4: 419

Crossref Google Scholar
4b C15-C24 and C25-C30: Desroy N. Le Roux R. Phansavath P. Chiummiento L. Bonini C. Genêt J.-P. Tetrahedron Lett. 2003, 44: 1763

Crossref Google Scholar
4c C1-C13: Le Roux R. Desroy N. Phansavath P. Genêt J.-P. Synlett 2005, 429

Crossref Google Scholar
4d C15-C30: Schmidt DR. Park PK. Leighton JL. Org. Lett. 2003, 5: 3535

Crossref Google Scholar
4e C1-C13: Keck GE. McLaws MD. Tetrahedron Lett. 2005, 46: 4911

Crossref Google Scholar
5 Park PK. O’Malley SJ. Schmidt DR. Leighton JL. J. Am. Chem. Soc. 2006, 128: 2796

Crossref Google Scholar
6 Evans DA. Gauchet-Prunet JA. J. Org. Chem. 1993, 58: 2446

Crossref Google Scholar
7 Lowik DWPM. Liskamp RMJ. Eur. J. Org. Chem. 2000, 1219

Crossref Google Scholar
8a Chow S. Kitching W. Tetrahedron: Asymmetry 2002, 13: 779

Crossref PubMed Google Scholar
8b Jacobsen EN. Acc. Chem. Res. 2000, 33: 421

Crossref PubMed Google Scholar
9a Scholl M. Ding S. Lee CW. Grubbs RH. Org. Lett. 1999, 1: 953

Google Scholar
9b Chatterjee AK. Grubbs RH. Angew. Chem. Int. Ed. 2002, 41: 3172

Google Scholar
10 The key step of the synthesis of amide 13 is an Evans aldol reaction with an aldehyde derived from the Roche ester: Clark DL. Heathcock CH. J. Org. Chem. 1993, 58: 5878

Crossref Google Scholar
11 Evans DA. Coleman PJ. Côté B. J. Org. Chem. 1997, 62: 788

Crossref Google Scholar
12a Ozawa T. Aoyagi S. Kibayashi C. J. Org. Chem. 2001, 66: 3338

Crossref Google Scholar
12b Barton DHR. Dorchak J. Jaszberenyi JCs. Tetrahedron 1992, 48: 7435

Crossref Google Scholar
13 Vincent A. Prunet J. Tetrahedron Lett. 2006, 47: 4075

Crossref Google Scholar
14 Frigerio M. Santagostino M. Sputore S. J. Org. Chem. 1999, 64: 4537

Crossref Google Scholar
15a Ohira S. Synth. Commun. 1989, 19: 561

Crossref Google Scholar
15b Müller S. Liepold B. Roth GJ. Bestmann HJ. Synlett 1996, 521

Crossref Google Scholar
15c Davies HML. Cantrell WR. Romines KR. Baum JS. Org. Synth. 1992, 70: 93

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

Crossref Google Scholar
17 Wipf P. Lim S. Angew. Chem. Int. Ed. 1993, 32: 1068

Google Scholar
18a Barbero A. Cuadrado P. Fleming I. Gonzalez AM. Pulido FJ. Sanchez A. J. Chem. Soc., Perkin Trans. 1 1995, 1525

Crossref Google Scholar
18b Fleming I. Newton T. Roessler F. J. Chem. Soc., Perkin Trans. 1 1981, 2527

Crossref Google Scholar
19 Uenishi J. Kawahama R. Yonemitsu O. J. Org. Chem. 1997, 62: 1691 ; this reaction was performed on a model compound

Crossref Google Scholar
20 Takai K. Nitta K. Utimoto K. J. Am. Chem. Soc. 1986, 108: 7408

Crossref Google Scholar
22 Morrill C. Grubbs RH. J. Org. Chem. 2003, 68: 6031

Google Scholar

21

This reaction has not been optimized.

23

Spectroscopic data for compound 23: ¹H NMR (400 MHz, CDCl₃): δ = 7.51 (dd, J = 7.9, 1.5 Hz, 2 H, Ph), 7.35-7.40 (m, 3 H, Ph), 7.27 (d, J = 8.6 Hz, 2 H, PMB), 6.86 (d, J = 8.6 Hz, 2 H, PMB), 5.94 (dd, J = 2.1, 1.3 Hz, 1 H, CH-15), 5.48 (s, 1 H, CHPh), 4.53 (d, J = 10.8 Hz, 1 H, CHHPh), 4.49 (d, J = 11.0 Hz, 1 H, CHHPh), 3.98-4.18 (m, 2 H, CH-7, CH-9), 3.78-3.82 (m, 1 H, CH-11), 3.79 (s, 3 H, OCH₃), 3.72 (dd, J = 9.6, 5.2 Hz, 1 H, CH-1), 3.63 (dd, J = 9.6, 3.0 Hz, 1 H, CH-1), 3.27 (dd, J = 8.7, 2.2 Hz, 1 H, CH-3), 2.35-2.48 (m, 2 H, CH₂-13), 1.87 (d, J = 1.2 Hz, 3 H, CH₃-14), 1.78-1.84 (m, 2 H, CH-2, CH-12), 1.30-1.75 (m, 10 H, CH-4, CH₂-5, CH₂-6, CH₂-8, CH₂-10, CH-12), 0.89-0.97 [m, 24 H, SiC(CH₃)₃, CH₃-2, CH₃-4], 0.09, 0.08, 0.06 [s, 12 H, Si(CH₃)₂]. ¹³C NMR (100 MHz, CDCl₃): δ = 147.6 (C-14), 158.9, 138.9, 131.6, 129.1, 128.5, 128.1, 126.0, 113.7 (Ar), 100.2 (CHPh), 83.6 (C-3), 75.9 (C-11), 74.9 (C-15), 74.5 (CH₂Ph), 73.0 (C-9), 67.9 (C-7), 65.0 (C-1), 55.3 (OCH₃), 43.3 (C-6), 38.6 (C-2), 37.5 (C-10), 36.3 (C-8), 35.6 (C-4), 35.1 (C-13), 33.9 (C-12), 29.6 (C-5), 26.0 [SiC(CH₃)₃], 24.0 (CH₃-14), 18.3, 18.1 (SiC), 14.7 (CH₃-2), 13.5 (CH₃-4), -4.1, -4.5, -5.3, -5.4 [Si(CH₃)₂]. HRMS (EI): m/z calcd for C₄₅H₇₅O₆I₁Si₂: 894.4147; found: 894.4155.