Chiral Preparation of C ₂-Symmetric 4-Cyclopentene-1,3-diol

Abstract

Optically pure C₂ -symmetric 4-cyclopentene-1,3-diol has been prepared in both enantiomeric forms from racemic (3aS*,4R*,7S*,7aS*)-3a,4,7,7a-tetrahydro-4,7-methano-1H-inden-1-one by employing lipase-mediated kinetic resolution as the key step. As a result, the known (3aS*,4R*,7S*,7aS*)-3a,4,7,7a-tetrahydro-4,7-methano-1H-inden-1-one is transformed into (1′S*,3′S*,3′aR*,4′S*,7′R*,7′aS*)- 2′,3′,3′a,4′,7′,7′a-hexahydro-3′-hydroxy-4′,7′-methano-1′H-inden-1′-yl benzoate, via stereo- and regioselective hydride reduction of epoxy ketone and sequential benzoylation, which is resolved under transesterification conditions in the presence of lipase. The hydride reduction of benzoate and acetate gives the corresponding chiral diols, which are further transformed into both enantiomers of C₂ -symmetric 4-cyclopentene-1,3-diol via a retro-Diels-Alder reaction.

enzymes - stereoselective synthesis - Diels-Alder reactions - diols - epoxides

References

<A NAME="RF01402SS-1">1</A> Kobayashi Y. Trends in Organic Chemistry  1998,  7:  27 

<A NAME="RF01402SS-2">2</A> Noyori R. Suzuki M. Angew. Chem. Int. Ed. Engl.  1984,  23:  847 

<A NAME="RF01402SS-3">3</A> Borthwick AD. Biggadike K. Tetrahedron  1992,  48:  571 

<A NAME="RF01402SS-4">4</A> Schoffers E. Golebiowski A. Johnson CR. Tetrahedron  1996,  52:  3769 

<A NAME="RF01402SS-5">5</A> Miura S. Kurozumi S. Toru T. Tanaka T. Kobayashi M. Matsubara S. Ishimoto S. Tetrahedron  1976,  32:  1893 

<A NAME="RF01402SS-6">6</A> Saddler JC. Donaldson RE. Fuchs PL. J. Am. Chem. Soc.  1981,  103:  2110 

<A NAME="RF01402SS-7">7</A> Donaldson RE. Fuchs PL. J. Am. Chem. Soc.  1981,  103:  2108 

<A NAME="RF01402SS-8A">8a</A> Rosenblum M. J. Am. Chem. Soc.  1957,  79:  3179 

<A NAME="RF01402SS-8B">8b</A> Non-hazardous synthesis of racemic dienone 7, see: Takano S. Moriya M. Tanaka K. Ogasawara K. Synthesis  1994,  687 

An exploitation of dienone 7 as a chiral synthon, see the following reviews:

<A NAME="RF01402SS-9A">9a</A> Ogasawara K. Pure Appl. Chem.  1994,  66:  2119 

<A NAME="RF01402SS-9B">9b</A> Ogasawara K. J. Syn. Org. Chem. Jpn.  1996,  54:  29 

<A NAME="RF01402SS-10">10</A> A pertinent monograph, see: Enzyme Catalysis in Organic Synthesis   Drauz K. Waldmann H. VCH; Weinheim: 1995. 

<A NAME="RF01402SS-11">11</A>

Preliminary results of this work were presented at The 5 ^th International Symposium on Biocatalysis and Biotransformation, Darmstadt: Germany, September 2-7, 2001, see abstracts p. 353.

<A NAME="RF01402SS-12">12</A> Chapman OL. Hess TC. J. Org. Chem.  1979,  44:  962 

<A NAME="RF01402SS-13">13</A> Quite recently, a similar regio- and stereoselective reduction of keto epoxide has been reported, see: Mehta G. Kumaran RS. Tetrahedron Lett.  2001,  42:  8097 

<A NAME="RF01402SS-14">14</A> Dols PPMA. Arnouts EG. Rohaan J. Klunder AJH. Zwanenburg B. Tetrahedron  1994,  50:  3473 

<A NAME="RF01402SS-15">15</A>

All of the lipases we used were commercially available from Amano Enzyme Inc., Japan. The origin of each lipase is summarized in the Table.

<A NAME="RF01402SS-16">16</A> Takano S. Moriya M. Ogasawara K. Synlett  1993,  601 

<A NAME="RF01402SS-17">17</A> cf: Kamikubo T. Ogasawara K. J. Chem. Soc., Chem. Commun.  1995,  1951