A New Access to the 6,8-Dioxabicyclo[3.2.1]octane
Ring System Using a Three-Component Reaction: Enantioselective Synthesis
of (+)-iso-exo-Brevicomin

Asmae Bouziane; Thomas Régnier; François Carreaux; Bertrand Carboni; Christian Bruneau; Jean-Luc Renaud

doi:10.1055/s-0029-1218561

RSS-Feed abonnieren

Bitte kopieren Sie die angezeigte URL und fügen sie dann in Ihren RSS-Reader ein.

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

Teilen / Bookmarken

Facebook Linkedin Weibo

PDF herunterladen

Synlett 2010(2): 207-210
DOI: 10.1055/s-0029-1218561

LETTER

A New Access to the 6,8-Dioxabicyclo[3.2.1]octane Ring System Using a Three-Component Reaction: Enantioselective Synthesis of (+)-iso-exo-Brevicomin

Asmae Bouziane^a, Thomas Régnier^a, François Carreaux*^a, Bertrand Carboni^a, Christian Bruneau^a, Jean-Luc Renaud^b
^a Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France
e-Mail: francois.carreaux@univ-rennes1.fr;
^b Laboratoire Chimie Moléculaire et Thioorganique, UMR CNRS 6507, 6 Bd du Maréchal Juin, 14050 Caen, France

Weitere Informationen

Publikationsverlauf

Received 9 October 2009
Publikationsdatum:
10. Dezember 2009 (online)

Abstract
Volltext
Referenzen

Lizenzen und Reprints Alle Artikel dieser Rubrik

Abstract

The combination of a catalytic hetero-Diels-Alder-allylboration sequence and a ruthenium-catalyzed isomerization of an allylic alcohol moiety as key steps open a new route for the asymmetric synthesis of 6,8-dioxabicyclo[3.2.1]octane subunits. The application of this strategy to the synthesis of (+)-iso-exo-brevicomin is also reported.

Key words

natural product - asymmetric catalysis - cycloaddition - boron - redox isomerization

References and Notes

1a Mori K. Tetrahedron 1989, 45: 3233

Suche in Google Scholar
1b Francke W. Schröder W. Curr. Org. Chem. 1999, 3: 407

Suche in Google Scholar
Some examples:
2a For palytoxin, see: Moore RE. Prog. Chem. Org. Nat. Prod. 1985, 48: 81

Suche in Google Scholar
2b For pinnatoxin A, see: Uemura D. Chou T. Haino T. Nagatsu A. Fukuzawa S. Zheng SZ. Chen HS. J. Am. Chem. Soc. 1995, 117: 1155

Suche in Google Scholar
2c For attenol A, see: Takada N. Suenaga K. Yamada K. Zheng S.-Z. Chen H.-S. Uemura D. Chem. Lett. 1999, 1025
2d For pteriatoxins, see: Takada N. Umemura N. Suenaga K. Uemura D. Tetrahedron Lett. 2001, 42: 3495

Suche in Google Scholar
2e For trichodermatide A, see: Sun Y. Tian L. Huang J. Ma H.-Y. Zheng Z. Lv A.-L. Yasukawa K. Pei Y.-H. Org. Lett. 2008, 10: 393

Suche in Google Scholar
3 Mitchell SS. Rhodes D. Bushman FD. Faulkner DJ. Org. Lett. 2000, 2: 1605

Crossref PubMed Suche in Google Scholar
4a Milroy L.-G. Zintalla G. Prencipe G. Michel P. Ley S. Gunaratnam M. Beltran M. Neidle S. Angew. Chem. Int. Ed. 2007, 46: 2493

Suche in Google Scholar
4b Milroy L.-G. Zintalla G. Loiseau F. Qian Z. Prencipe G. Pepper C. Fegan C. Ley SV. ChemMedChem 2008, 3: 1922

Suche in Google Scholar
5a Burke SD. Müller N. Beaudry CM. Org. Lett. 1999, 1: 1827

Suche in Google Scholar
5b Marvin CC. Voight EA. Suh JM. Paradise CL. Burke SD. J. Org. Chem. 2008, 73: 8452

Suche in Google Scholar
For the formation of dioxabicyclo[3.2.1]octane structure via catalyzed cycloisomerization, see:
6a Antoniotti S. Genin E. Michelet V. Genet JP. J. Am. Chem. Soc. 2005, 127: 9976

Suche in Google Scholar
6b Liu B. De Brabander JK. Org. Lett. 2006, 8: 4907

Suche in Google Scholar
6c Ramana CV. Patel P. Gonnade RG. Tetrahedron Lett. 2007, 48: 4771

Suche in Google Scholar
6d Diéguez-Vasquez A. Tzschuscke CC. Lam WY. Ley SV. Angew. Chem. Int. Ed. 2008, 47: 209

Suche in Google Scholar
6e Ramana CV. Induvadana B. Tetrahedron Lett. 2009, 50: 271

Suche in Google Scholar
For some reviews on synthesis of bridged bicyclic ketals, see:
7a Kotsuki H. Synlett 1992, 97
7b Kiyota H. Top. Heterocycl. Chem. 2006, 5: 65

Suche in Google Scholar
8 Gademan K. Chavez DE. Jacobsen EN. Angew. Chem. Int. Ed. 2002, 41: 3059

Crossref PubMed Suche in Google Scholar
9a Deligny M. Carreaux F. Toupet L. Carboni B. Adv. Synth. Catal. 2003, 345: 1215

Suche in Google Scholar
9b Gao X. Hall DG. J. Am. Chem. Soc. 2003, 125: 9308

Suche in Google Scholar
9c Gao X. Hall DG. Deligny M. Favre A. Carreaux F. Carboni B. Chem. Eur. J. 2006, 12: 3132

Suche in Google Scholar
10a Deligny M. Carreaux F. Carboni B. Synlett 2005, 1462
10b Gao X. Hall DG. J. Am. Chem. Soc. 2005, 127: 1628

Suche in Google Scholar
10c Carreaux F. Favre A. Carboni B. Rouaud I. Boustie J. Tetrahedron Lett. 2006, 47: 4545

Suche in Google Scholar
10d Favre A. Carreaux F. Deligny M. Carboni B. Eur. J. Org. Chem. 2008, 4900
10e Penner M. Rauniyar V. Kaspar LT. Hall DG. J. Am. Chem. Soc. 2009, 131: 14216

Suche in Google Scholar
13 Francke W. Schröder F. Philipp P. Meyer H. Sinnwell V. Gries G. Bioorg. Med. Chem. 1996, 4: 363

Crossref PubMed Suche in Google Scholar
14a Mori K. Takikawa H. Nishimura Y. Horikiri H. Liebigs Ann./Recl. 1997, 327
14b Taniguchi T. Takeuchi M. Ogasawara K. Tetrahedron: Asymmetry 1998, 9: 1451

Suche in Google Scholar
14c De Sousa AL. Resck IS. J. Braz. Chem. Soc. 2002, 13: 233

Suche in Google Scholar
14d Prasad KR. Anbarasan P. Tetrahedron: Asymmetry 2007, 18: 1419

Suche in Google Scholar
16a Using isomerization of allylic alcohols, see: Ito M. Kitahara S. Ikariya T. J. Am. Chem. Soc. 2005, 127: 6172

Suche in Google Scholar
16b Using isomerization of propargylic alcohols, see: Trost BM. Livingston RC. J. Am. Chem. Soc. 2008, 130: 11970

Suche in Google Scholar
For reviews, see:
17a Uma R. Crévisy C. Grée R. Chem. Rev. 2003, 103: 27

Suche in Google Scholar
17b Cadierno V. Crochet P. Gimeno J. Synlett 2008, 1105
18 Bouziane A. Carboni B. Bruneau C. Carreaux F. Renaud J.-L. Tetrahedron 2008, 64: 11745

Crossref Suche in Google Scholar
21 Gravel M. Touré BB. Hall DG. Org. Prep. Proced. Int. 2004, 36: 573

Crossref Suche in Google Scholar

11

General Procedure and Selected Characterization Data
To a stirred solution of 3 (0.3 mmol) in CH₂Cl₂ (3 mL) at 0 ˚C was added BF₃˙OEt₂ (0.33 mmol). After 10 min, the resulting solution was warmed to r.t. and stirred for 90 min (excepted in the case of 3d). The reaction mixture was quenched with sat. aq NaHCO₃ (1 mL), and the aqueous phase was extracted with Et₂O (2 × 2 mL). The combined organic phases were washed with brine, dried over MgSO₄, filtrated, and concentrated under reduced pressure. Compounds 4 were purified by flash chromatography on silica gel (210-400 mesh).
Compound 4d was obtained as a colorless oil (95%). [α]_D ^²5 +33.5 (c 1.75, CH₂Cl₂). ^¹H NMR (300 MHz, CDCl₃): δ = 1.03 (s, 9 H), 1.91-1.97 (m, 1 H), 2.33-2.42 (m, 1 H), 4.26 (d, 1 H, J = 8.4 Hz), 4.44 (d, 1 H, J = 8.8 Hz), 4.47 (d, 1 H, J = 4.9 Hz), 5.50-5.52 (m, 1 H), 5.60-5.63 (m, 1 H), 5.98-6.04 (m, 1 H), 7.20-7.28 (m, 7 H), 7.35-7.49 (m, 6 H), 7.66-7.71 (m, 2 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 19.4, 26.9, 33.8, 72.0, 75.0, 88.7, 100.9, 124.3, 127.4, 127.5, 127.6, 127.7, 128.0, 128.9, 129.7, 129.8, 133.0, 134.0, 135.9, 136.0, 141.4. Anal. Calcd for C₂₉H₃₂O₃Si: C, 76.28; H, 7.06. Found: C, 76.35; H, 7.01.

12

Compound 8 was obtained as colorless oil (87%). [α]_D ^²5 +20.3 (c 1.30, CH₂Cl₂). ^¹H NMR (300 MHz, CDCl₃): δ = 1.03 (s, 9 H), 1.45-1.88 (m, 4 H), 2.29 (br s, 1 H), 3.60-3.63 (m, 1 H), 4.04 (d, 1 H, J = 7.3 Hz), 4.20-4.25 (m, 1 H), 4.49 (d, 1 H, J = 7.3 Hz), 5.32 (br s, 1 H), 7.21-7.33 (m, 7 H), 7.35-7.48 (m, 6 H), 7.61-7.69 (m, 2 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 19.4, 23.8, 26.8, 26.9, 66.7, 76.1, 77.2, 78.9, 81.5, 102.5, 127.4, 127.6, 127.8, 128.1, 129.6, 129.8, 133.1, 133.8, 135.9, 136.0, 140.9. Anal. Calcd for C₂₉H₃₄O₄Si: C, 73.38; H, 7.22. Found: C, 73.37; H, 7.11.

15

The ee was measured by GC analysis using a chiral stationary phase (Varian WCOT Fused Silica 25 × 0.25 mm coated CP Chirasil-dex CB DF = 0.25).

19

1-Phenylpropan-1-one can be obtained from the corresponding allylic alcohol in 97% yield with only 2 mol% of [RuCp*(MeCN)₃][PF₆] in toluene at r.t. These new conditions represent an improvement of the previously described process with this catalyst.

20

Characterization Data for Key Synthetic Intermediates
Compound 3e was obtained from 1 in 70% yield as a colorless oil. [α]_D ^²5 +72 (c 0.59, CH₂Cl₂). ^¹H NMR (300 MHz, CDCl₃): δ = 1.18-1.25 (m, 6 H), 2.19-2.22 (m, 2 H), 2.72 (br s, 1 H), 3.53 (dq, 1 H, J = 7.1, 9.3 Hz), 3.69-3.72 (m, 1 H), 3.96 (dq, 1 H, J = 7.1, 9.3 Hz), 3.98-4.03 (m, 1 H), 4.72 (dd, 1 H, J = 4.8, 6.1 Hz), 5.60-5.63 (m, 1 H), 5.78-5.80 (m, 1 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 15.2, 18.6, 31.1, 64.4, 69.6, 78.8, 98.5, 124.9, 126.1. HRMS (EI): m/z [M -˙OCH₂CH₃]⁺ calcd for C₇H₁₁O₂: 127.0759; found: 127.0755.
Compound 12 was obtained as colorless oil (mixture of diastereomers, 63%). ^¹H NMR (300 MHz, CDCl₃): δ = 1.20 (d, 3 H, J = 5.9 Hz), 1.35-1.70 (m, 6 H), 1.81 (br s, 1 H), 2.68 (br s, 1 H), 3.40-3.43 (m, 2 H), 4.09-4.12 (m, 1 H), 4.43 (d, 1 H, J = 11.5 Hz), 4.68 (d, 1 H, J = 11.5 Hz), 5.11 (dd, 1 H, J = 1.2, 10.4 Hz), 5.23 (d, 1 H, J = 17.2 Hz), 5.88 (ddd, 1 H, J = 6.2, 10.4, 17.2 Hz), 7.26-7.43 (m, 5 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 15.5, 21.3, 21.4, 32.5, 32.6, 36.9, 71.0, 73.0, 73.1, 74.8, 74.9, 78.3, 78.4, 114.5, 114.6, 127.7, 127.8, 128.5, 138.3, 141.1, 141.2. ESI-HRMS: m/z [M + Na]⁺ calcd for C₁₆H₂₄O₃Na: 287.1623; found: 287.1623.
(+)-Iso-exo-brevicomin was obtained as a colorless oil (highly volatile, 60%): [α]_D ^²5 +53 (c 0.3, CHCl₃); lit.^¹4d [α]_D +54 (c 0.5, CHCl₃). ^¹H NMR (300 MHz, CDCl₃): δ = 0.96 (t, 3 H, J = 7.9 Hz), 1.18 (d, 3 H, J = 6.5 Hz), 1.43-1.95 (m, 8 H), 4.06 (br s, 1 H), 4.22 (q, 1 H, J = 6.5 Hz). ^¹³C NMR (75 MHz, CDCl₃): δ = 7.3, 17.1, 21.6, 28.0, 30.6, 33.5, 75.5, 79.9, 109.5. Anal. Calcd for C₉H₁₆O₂: C, 69.19; H, 10.32. Found: C, 69.27; H, 10.41.