Synthesis of Functionalized Pentalenes via Carbonyl-Ene Reaction and Enzymatic Kinetic Resolution

Timo Anderl; Marc Emo; Sabine Laschat; Angelika Baro; Wolfgang Frey

doi:10.1055/s-2008-1067012

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Synthesis 2008(10): 1619-1627
DOI: 10.1055/s-2008-1067012

PAPER

Synthesis of Functionalized Pentalenes via Carbonyl-Ene Reaction and Enzymatic Kinetic Resolution

Timo Anderl, Marc Emo, Sabine Laschat*, Angelika Baro, Wolfgang Frey
Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
Fax: +49(711)68564285; e-Mail: sabine.laschat@oc.uni-stuttgart.de;

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Publication History

Received 5 February 2008
Publication Date:
11 April 2008 (online)

Abstract
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Abstract

The synthesis of functionalized pentalene derivatives is described. Bicyclo[3.3.0]octane-3,7-dione 5 (Weiss diketone) was converted in six steps into the silyl-protected 3-methylbicyclo[3.3.0]octenol 6, which was submitted to Lewis acid catalyzed carbonyl-ene reactions with trioxane yielding the primary alcohol 7 with exocyclic double bond in high yield. By subsequent kinetic resolution with lipases compound 7 was enantiomerically enriched (up to 94% ee). It was also demonstrated that compound 7 could be functionalized by hydroboration and oxidative workup to give the trihydroxy pentalene 8 as well as by chain extension to the pentalene 23.

Key words

bicyclo[3.3.0]octanedione - hydroboration - lipases - primary alcohols - pentalene

References

Reviews on pentalene syntheses:
1a Haag R. de Meijere A. Top. Curr. Chem. 1998, 196: 137

Google Scholar
1b Ghatak UR. Proc. Indian Nat. Sci. Acad. A 1995, 61: 21

Google Scholar
1c Negishi E. Pure Appl. Chem. 1992, 64: 323

Google Scholar
1d Hudlicky T. Sinai-Zingde G. Natchus MG. Ranu BC. Papadopolous P. Tetrahedron 1987, 43: 5685

Google Scholar
1e Demuth M. In Modern Synthetic Methods Vol. 4: Scheffold R. Springer; Berlin: 1986. p.89-124

Google Scholar
1f Ley SV. Chem. Ind. (London) 1985, 101

Google Scholar
Reviews on polyquinanes:
2a Mehta G. Srikrishna A. Chem. Rev. 1997, 97: 671

Crossref PubMed Google Scholar
2b Paquette LA. Top. Curr. Chem. 1984, 119: 1

Crossref PubMed Google Scholar
2c Ramaiah M. Synthesis 1984, 529

Crossref PubMed Google Scholar
2d Trost BM. Chem. Soc. Rev. 1982, 11: 141

Crossref PubMed Google Scholar
2e Paquette LA. Top. Curr. Chem. 1979, 79: 41

Crossref PubMed Google Scholar
For macrolactams such as cylindramide, see:
2f Kanazawa S. Fusetani N. Matsunaga S. Tetrahedron Lett. 1993, 34: 1065

Crossref PubMed Google Scholar
2g Cramer N. Laschat S. Baro A. Schwalbe H. Richter C. Angew. Chem. Int. Ed. 2005, 44: 820 ; Angew. Chem. 2005, 117, 831

Crossref PubMed Google Scholar
2h Cramer N. Buchweitz M. Laschat S. Frey W. Baro A. Mathieu D. Richter C. Schwalbe H. Chem. Eur. J. 2006, 12: 2488 ; and references cited therein

Crossref PubMed Google Scholar
3 Triquinane synthesis: Son SU. Park KH. Lee SJ. Kim BM. Chung YK. Synlett 2003, 1101

Article in Thieme Connect Google Scholar
4a Harrington-Frost NM. Pattenden G. Tetrahedron Lett. 2000, 41: 403

Google Scholar
4b Devin P. Fensterbank L. Malacria M. J. Org. Chem. 1998, 63: 6764

Google Scholar
4c Sha C.-K. Santhosh KC. Lih S.-H. J. Org. Chem. 1998, 63: 2699

Google Scholar
4d Enholm EJ. Jia ZJ. J. Org. Chem. 1997, 62: 174

Google Scholar
4e Jasperse CP. Curran DP. Fevig TL. Chem. Rev. 1991, 91: 1237

Google Scholar
5a Renaud J.-L. Aubert C. Malacria M. Tetrahedron 1999, 55: 5113

Article in Thieme Connect Google Scholar
5b Seo J. Fain H. Blanc J.-B. Montgomery J. J. Org. Chem. 1999, 64: 6060

Article in Thieme Connect Google Scholar
5c Tormo J. Moyano A. Pericas MA. Riera A. J. Org. Chem. 1997, 62: 4851

Article in Thieme Connect Google Scholar
5d Meyer C. Marek I. Normant J.-F. Tetrahedron Lett. 1996, 37: 857

Article in Thieme Connect Google Scholar
5e Tormo J. Verdaguer X. Moyano A. Pericas MA. Riera A. Tetrahedron 1996, 52: 14021

Article in Thieme Connect Google Scholar
5f Saitoh F. Mori M. Okamura K. Date T. Tetrahedron 1995, 51: 4439

Article in Thieme Connect Google Scholar
5g Piers E. Orellana A. Synthesis 2001, 2138

Article in Thieme Connect Google Scholar
6 Bahu G. Sridar V. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem. 1996, 35: 711

Google Scholar
7a Laschat S. Becheanu A. Bell T. Baro A. Synlett 2005, 2547

Google Scholar
7b Park KH. Chung YK. Synlett 2005, 545

Google Scholar
7c Rodriguez Rivero M. Adrio J. Carretero JC. Synlett 2005, 26

Google Scholar
7d Gibson SE. Mainolfi N. Angew. Chem. Int. Ed. 2005, 44: 3022 ; Angew. Chem. 2005, 117, 3082

Google Scholar
7e Bonaga LVR. Krafft ME. Tetrahedron 2004, 60: 9795

Google Scholar
7f Gibson SE. Stevenazzi A. Angew. Chem. Int. Ed. 2003, 42: 1800 ; Angew. Chem. 2003, 115, 1844

Google Scholar
7g Hanson BE. Comments Inorg. Chem. 2002, 23: 289

Google Scholar
7h Brummond KM. Kent JL. Tetrahedron 2000, 56: 3263

Google Scholar
7i Fletcher AJ. Christie SDR. J. Chem. Soc., Perkin Trans. 1 2000, 1657

Google Scholar
7j Chung YK. Coord. Chem. Rev. 1999, 188: 297

Google Scholar
8 Becheanu A. Bell T. Laschat S. Baro A. Frey W. Steinke N. Fischer P. Z. Naturforsch. 2006, 61b: 589

Google Scholar
9 Becheanu A. Baro A. Laschat S. Frey W. Eur. J. Org. Chem. 2006, 2215

Crossref Google Scholar
10a Bertz SH. Cook JM. Gawish A. Weiss U. Org. Synth. 1986, 64: 27

Crossref Google Scholar
10b Weiss U. Edwards JM. Tetrahedron Lett. 1968, 4885

Crossref Google Scholar
Reviews on carbonyl-ene reactions:
11a Mikami K. Nakai T. In Catalytic Asymmetric Synthesis 2nd ed.: Ojima I. Wiley-VCH; New York: 2000. p.543-568

Article in Thieme Connect Google Scholar
11b Dias LC. Curr. Org. Chem. 2000, 4: 305

Article in Thieme Connect Google Scholar
11c Johnson JS. Evans DA. Acc. Chem. Res. 2000, 33: 325

Article in Thieme Connect Google Scholar
11d Mikami K. Pure Appl. Chem. 1996, 68: 639

Article in Thieme Connect Google Scholar
11e Berrisford DJ. Bolm C. Angew. Chem., Int. Ed. Engl. 1995, 34: 1717 ; Angew. Chem. 1995, 107, 1862

Article in Thieme Connect Google Scholar
11f Mikami K. Shimizu M. Chem. Rev. 1992, 92: 1021

Article in Thieme Connect Google Scholar
11g Mikami K. Terada M. Narisawa S. Nakai T. Synlett 1992, 255

Article in Thieme Connect Google Scholar
12a Mikami K. Yoshida A. Matsumoto Y. Tetrahedron Lett. 1996, 37: 8515

Crossref Google Scholar
12b Mikami K. Yoshida A. Synlett 1995, 29

Crossref Google Scholar
12c Mikami K. Terada M. Narisawa S. Nakai T. Org. Synth. 1993, 71: 14

Crossref Google Scholar
13 Whitesell JK. Minton MA. J. Am. Chem. Soc. 1986, 108: 6802

Crossref Google Scholar
14 Piers E. Karunaratne V. Can. J. Chem. 1989, 67: 160

Crossref Google Scholar
15 Vaulont I. Gais H.-J. Reuter N. Schmitz E. Ossenkamp RKL. Eur. J. Org. Chem. 1998, 805

Crossref Google Scholar
17 Camps P. Lukach AE. Vázquez S. Tetrahedron 2001, 57: 2419

Crossref Google Scholar
18a Clive DLJ. Tao Y. Khodabocus A. Wu Y.-J. Angoh AG. Bennett SM. Boddy CN. Bordeleau L. Kellner D. Kleiner G. Middleton DS. Nichols CJ. Richardson SR. Vernon PG. J. Am. Chem. Soc. 1994, 116: 11275

Article in Thieme Connect Google Scholar
18b Hudlicky T. Kwart LD. Tiedje MH. Ranu BC. Short RP. Frazier JO. Rigby HL. Synthesis 1986, 716

Article in Thieme Connect Google Scholar
19a Blomquist AT. Himics RJ. J. Org. Chem. 1968, 33: 1156

Crossref Google Scholar
19b Yang NC. Yang D.-DH. Ross CB. J. Am. Chem. Soc. 1959, 81: 133

Crossref Google Scholar
19c Snider BB. Cordova R. Price RT. J. Org. Chem. 1982, 47: 3643

Crossref Google Scholar
19d Snider BB. Rodini DJ. Kirk TC. Cordova R. J. Am. Chem. Soc. 1982, 104: 555

Crossref Google Scholar
20 Maruoka K. Concepcion AB. Murase N. Oishi M. Hirayama N. Yamamoto H. J. Am. Chem. Soc. 1993, 115: 3943

Crossref Google Scholar
21 Bornscheuer UT. Kazlauskas RJ. Hydrolases in Organic Synthesis 2nd ed.: Wiley-VCH; Weinheim: 2006. p.106-113

Google Scholar
22 Tominaga H. Maezaki N. Yanai M. Kojima N. Urabe D. Ueki R. Tanaka T. Eur. J. Org. Chem. 2006, 1422

Crossref Google Scholar
23 Ebel H. Polborn K. Steglich W. Eur. J. Org. Chem. 2002, 2905

Crossref Google Scholar
24 Sankaranarayanan S. Chattopadhyay S. Tetrahedron: Asymmetry 1998, 9: 2627

Crossref Google Scholar
25 Iranpoor N. Firouzabadi H. Aghapour Gh. Vaezzadeh AR. Tetrahedron 2002, 58: 8689

Crossref Google Scholar
26 Fujimori I. Mita T. Maki K. Shiro M. Sato A. Furusho S. Kanai M. Shibasaki M. J. Am. Chem. Soc. 2006, 128: 16438

Crossref Google Scholar
27 Dandapani S. Jeske M. Curran DP. J. Org. Chem. 2005, 70: 9447

Crossref Google Scholar

16

CCDC-676656 contains all crystallographic details of this publication and is available free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html or can be ordered from the following address: Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB21EZ; Fax: +44 1223 336 033; or E-mail: deposit@ccdc.cam.ac.uk.