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

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.

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

References

Reviews on pentalene syntheses:

<A NAME="RZ04108SS-1A">1a</A> Haag R. de Meijere A. Top. Curr. Chem.  1998,  196:  137 

<A NAME="RZ04108SS-1B">1b</A> Ghatak UR. Proc. Indian Nat. Sci. Acad. A  1995,  61:  21 

<A NAME="RZ04108SS-1C">1c</A> Negishi E. Pure Appl. Chem.  1992,  64:  323 

<A NAME="RZ04108SS-1D">1d</A> Hudlicky T. Sinai-Zingde G. Natchus MG. Ranu BC. Papadopolous P. Tetrahedron  1987,  43:  5685 

<A NAME="RZ04108SS-1E">1e</A> Demuth M. In Modern Synthetic Methods   Vol. 4:  Scheffold R. Springer; Berlin: 1986.  p.89-124  

<A NAME="RZ04108SS-1F">1f</A> Ley SV. Chem. Ind. (London)  1985,  101 

Reviews on polyquinanes:

<A NAME="RZ04108SS-2A">2a</A> Mehta G. Srikrishna A. Chem. Rev.  1997,  97:  671 

<A NAME="RZ04108SS-2B">2b</A> Paquette LA. Top. Curr. Chem.  1984,  119:  1 

<A NAME="RZ04108SS-2C">2c</A> Ramaiah M. Synthesis  1984,  529 

<A NAME="RZ04108SS-2D">2d</A> Trost BM. Chem. Soc. Rev.  1982,  11:  141 

<A NAME="RZ04108SS-2E">2e</A> Paquette LA. Top. Curr. Chem.  1979,  79:  41 

For macrolactams such as cylindramide, see:

<A NAME="RZ04108SS-2F">2f</A> Kanazawa S. Fusetani N. Matsunaga S. Tetrahedron Lett.  1993,  34:  1065 

<A NAME="RZ04108SS-2G">2g</A> Cramer N. Laschat S. Baro A. Schwalbe H. Richter C. Angew. Chem. Int. Ed.  2005,  44:  820 ; Angew. Chem. 2005, 117, 831

<A NAME="RZ04108SS-2H">2h</A> 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

<A NAME="RZ04108SS-3">3</A> Triquinane synthesis: Son SU. Park KH. Lee SJ. Kim BM. Chung YK. Synlett  2003,  1101 

<A NAME="RZ04108SS-4A">4a</A> Harrington-Frost NM. Pattenden G. Tetrahedron Lett.  2000,  41:  403 

<A NAME="RZ04108SS-4B">4b</A> Devin P. Fensterbank L. Malacria M. J. Org. Chem.  1998,  63:  6764 

<A NAME="RZ04108SS-4C">4c</A> Sha C.-K. Santhosh KC. Lih S.-H. J. Org. Chem.  1998,  63:  2699 

<A NAME="RZ04108SS-4D">4d</A> Enholm EJ. Jia ZJ. J. Org. Chem.  1997,  62:  174 

<A NAME="RZ04108SS-4E">4e</A> Jasperse CP. Curran DP. Fevig TL. Chem. Rev.  1991,  91:  1237 

<A NAME="RZ04108SS-5A">5a</A> Renaud J.-L. Aubert C. Malacria M. Tetrahedron  1999,  55:  5113 

<A NAME="RZ04108SS-5B">5b</A> Seo J. Fain H. Blanc J.-B. Montgomery J. J. Org. Chem.  1999,  64:  6060 

<A NAME="RZ04108SS-5C">5c</A> Tormo J. Moyano A. Pericas MA. Riera A. J. Org. Chem.  1997,  62:  4851 

<A NAME="RZ04108SS-5D">5d</A> Meyer C. Marek I. Normant J.-F. Tetrahedron Lett.  1996,  37:  857 

<A NAME="RZ04108SS-5E">5e</A> Tormo J. Verdaguer X. Moyano A. Pericas MA. Riera A. Tetrahedron  1996,  52:  14021 

<A NAME="RZ04108SS-5F">5f</A> Saitoh F. Mori M. Okamura K. Date T. Tetrahedron  1995,  51:  4439 

<A NAME="RZ04108SS-5G">5g</A> Piers E. Orellana A. Synthesis  2001,  2138 

<A NAME="RZ04108SS-6">6</A> Bahu G. Sridar V. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem.  1996,  35:  711 

<A NAME="RZ04108SS-7A">7a</A> Laschat S. Becheanu A. Bell T. Baro A. Synlett  2005,  2547 

<A NAME="RZ04108SS-7B">7b</A> Park KH. Chung YK. Synlett  2005,  545 

<A NAME="RZ04108SS-7C">7c</A> Rodriguez Rivero M. Adrio J. Carretero JC. Synlett  2005,  26 

<A NAME="RZ04108SS-7D">7d</A> Gibson SE. Mainolfi N. Angew. Chem. Int. Ed.  2005,  44:  3022 ; Angew. Chem. 2005, 117, 3082

<A NAME="RZ04108SS-7E">7e</A> Bonaga LVR. Krafft ME. Tetrahedron  2004,  60:  9795 

<A NAME="RZ04108SS-7F">7f</A> Gibson SE. Stevenazzi A. Angew. Chem. Int. Ed.  2003,  42:  1800 ; Angew. Chem. 2003, 115, 1844

<A NAME="RZ04108SS-7G">7g</A> Hanson BE. Comments Inorg. Chem.  2002,  23:  289 

<A NAME="RZ04108SS-7H">7h</A> Brummond KM. Kent JL. Tetrahedron  2000,  56:  3263 

<A NAME="RZ04108SS-7I">7i</A> Fletcher AJ. Christie SDR. J. Chem. Soc., Perkin Trans. 1  2000,  1657 

<A NAME="RZ04108SS-7J">7j</A> Chung YK. Coord. Chem. Rev.  1999,  188:  297 

<A NAME="RZ04108SS-8">8</A> Becheanu A. Bell T. Laschat S. Baro A. Frey W. Steinke N. Fischer P. Z. Naturforsch.  2006,  61b:  589 

<A NAME="RZ04108SS-9">9</A> Becheanu A. Baro A. Laschat S. Frey W. Eur. J. Org. Chem.  2006,  2215 

<A NAME="RZ04108SS-10A">10a</A> Bertz SH. Cook JM. Gawish A. Weiss U. Org. Synth.  1986,  64:  27 

<A NAME="RZ04108SS-10B">10b</A> Weiss U. Edwards JM. Tetrahedron Lett.  1968,  4885 

Reviews on carbonyl-ene reactions:

<A NAME="RZ04108SS-11A">11a</A> Mikami K. Nakai T. In Catalytic Asymmetric Synthesis   2nd ed.:  Ojima I. Wiley-VCH; New York: 2000.  p.543-568  

<A NAME="RZ04108SS-11B">11b</A> Dias LC. Curr. Org. Chem.  2000,  4:  305 

<A NAME="RZ04108SS-11C">11c</A> Johnson JS. Evans DA. Acc. Chem. Res.  2000,  33:  325 

<A NAME="RZ04108SS-11D">11d</A> Mikami K. Pure Appl. Chem.  1996,  68:  639 

<A NAME="RZ04108SS-11E">11e</A> Berrisford DJ. Bolm C. Angew. Chem., Int. Ed. Engl.  1995,  34:  1717 ; Angew. Chem. 1995, 107, 1862

<A NAME="RZ04108SS-11F">11f</A> Mikami K. Shimizu M. Chem. Rev.  1992,  92:  1021 

<A NAME="RZ04108SS-11G">11g</A> Mikami K. Terada M. Narisawa S. Nakai T. Synlett  1992,  255 

<A NAME="RZ04108SS-12A">12a</A> Mikami K. Yoshida A. Matsumoto Y. Tetrahedron Lett.  1996,  37:  8515 

<A NAME="RZ04108SS-12B">12b</A> Mikami K. Yoshida A. Synlett  1995,  29 

<A NAME="RZ04108SS-12C">12c</A> Mikami K. Terada M. Narisawa S. Nakai T. Org. Synth.  1993,  71:  14 

<A NAME="RZ04108SS-13">13</A> Whitesell JK. Minton MA. J. Am. Chem. Soc.  1986,  108:  6802 

<A NAME="RZ04108SS-14">14</A> Piers E. Karunaratne V. Can. J. Chem.  1989,  67:  160 

<A NAME="RZ04108SS-15">15</A> Vaulont I. Gais H.-J. Reuter N. Schmitz E. Ossenkamp RKL. Eur. J. Org. Chem.  1998,  805 

<A NAME="RZ04108SS-16">16</A>

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: [phone]; or E-mail: [e-mail].

<A NAME="RZ04108SS-17">17</A> Camps P. Lukach AE. Vázquez S. Tetrahedron  2001,  57:  2419 

<A NAME="RZ04108SS-18A">18a</A> 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 

<A NAME="RZ04108SS-18B">18b</A> Hudlicky T. Kwart LD. Tiedje MH. Ranu BC. Short RP. Frazier JO. Rigby HL. Synthesis  1986,  716 

<A NAME="RZ04108SS-19A">19a</A> Blomquist AT. Himics RJ. J. Org. Chem.  1968,  33:  1156 

<A NAME="RZ04108SS-19B">19b</A> Yang NC. Yang D.-DH. Ross CB. J. Am. Chem. Soc.  1959,  81:  133 

<A NAME="RZ04108SS-19C">19c</A> Snider BB. Cordova R. Price RT. J. Org. Chem.  1982,  47:  3643 

<A NAME="RZ04108SS-19D">19d</A> Snider BB. Rodini DJ. Kirk TC. Cordova R. J. Am. Chem. Soc.  1982,  104:  555 

<A NAME="RZ04108SS-20">20</A> Maruoka K. Concepcion AB. Murase N. Oishi M. Hirayama N. Yamamoto H. J. Am. Chem. Soc.  1993,  115:  3943 

<A NAME="RZ04108SS-21">21</A> Bornscheuer UT. Kazlauskas RJ. Hydrolases in Organic Synthesis   2nd ed.:  Wiley-VCH; Weinheim: 2006.  p.106-113  

<A NAME="RZ04108SS-22">22</A> Tominaga H. Maezaki N. Yanai M. Kojima N. Urabe D. Ueki R. Tanaka T. Eur. J. Org. Chem.  2006,  1422 

<A NAME="RZ04108SS-23">23</A> Ebel H. Polborn K. Steglich W. Eur. J. Org. Chem.  2002,  2905 

<A NAME="RZ04108SS-24">24</A> Sankaranarayanan S. Chattopadhyay S. Tetrahedron: Asymmetry  1998,  9:  2627 

<A NAME="RZ04108SS-25">25</A> Iranpoor N. Firouzabadi H. Aghapour Gh. Vaezzadeh AR. Tetrahedron  2002,  58:  8689 

<A NAME="RZ04108SS-26">26</A> Fujimori I. Mita T. Maki K. Shiro M. Sato A. Furusho S. Kanai M. Shibasaki M. J. Am. Chem. Soc.  2006,  128:  16438 

<A NAME="RZ04108SS-27">27</A> Dandapani S. Jeske M. Curran DP. J. Org. Chem.  2005,  70:  9447