A Semi-Pinacol Rearrangement Approach to Bicyclo[3.2.1]octan-2-ones and Bicyclo[3.2.1]octan-3-ones

Abstract

A diastereoselective approach to bicyclo[3.2.1]octan-2-ones and -3-ones is achieved by means of the semi-pinacol rearrangement of 2,3-epoxy silyl ethers. The key 1,2-migration is stereospecific. This method is easily amenable to an enantioselective synthesis by utilizing nonracemic norcamphor and related compounds.

Key words

rearrangement - ring expansion - epoxides - stereoselectivity

References and Notes

• For reviews on oxyallyls, see:
• 1a Noyori R. Hayakawa Y. Org. React.  1983,  29:  163 
• 1b Hoffmann HMR. Angew. Chem., Int. Ed. Engl.  1984,  23:  1 
• 1c Mann J. Tetrahedron  1986,  42:  4611 
• 1d Hosomi A. Tominaga Y. In Comprehensive Organic Synthesis   Vol. 5:  Trost BM. Fleming I. Pergamon; Oxford: 1991.  Chap. 5.1.
• 1e Rigby JH. Pigge FC. Org. React.  1997,  51:  351 
• 1f Harmata M. Tetrahedron  1997,  53:  6235 
• 1g Cha JK. Oh J. Curr. Org. Chem.  1998,  2:  217 
• 1h Harmata M. Acc. Chem. Res.  2001,  34:  595 
• For reviews on enantioselective cycloadditions, see:
• 2a Harmata M. Adv. Synth. Catal.  2006,  348:  2297 
• 2b See also: Hartung IV. Hoffmann HMR. Angew. Chem. Int. Ed.  2004,  43:  1934 
• 3 Harmata M. Ghosh SK. Hong X. Wacharasindhu S. Kirchhoefer P. J. Am. Chem. Soc.  2003,  125:  2058 
• 4 Huang J. Hsung RP. J. Am. Chem. Soc.  2005,  127:  50 
• 5a Davies HML. Dai X. J. Am. Chem. Soc.  2004,  126:  2692 
• 5b Dai X. Davies HML. Adv. Synth. Catal.  2006,  348:  2449 
• 6a Maruoka K. Hasegawa M. Yamamoto H. Suzuki K. Shimazaki M. Tsuchihashi G.-i. J. Am. Chem. Soc.  1986,  108:  3827 
• 6b Suzuki K. Shimazaki M. Tsuchihashi G.-i. Tetrahedron Lett.  1986,  27:  6237 
• 6c Suzuki K. Matsumoto T. Tomooka K. Matsumoto K. Tsuchihashi G.-i. Chem. Lett.  1987,  113 
• 6d Suzuki K. Miyazawa M. Tsuchihashi G.-i. Tetrahedron Lett.  1987,  28:  3515 
• 6e Shimazaki M. Hara H. Suzuki K. Tsuchihashi G.-i. Tetrahedron Lett.  1987,  28:  5891 
• 6f Suzuki K. Miyazawa M. Shimazaki M. Tsuchihashi G.-i. Tetrahedron  1988,  44:  4061 
• 6g Suzuki K. J. Synth. Org. Chem. Jpn.  1988,  46:  49 
• 6h Shimazaki M. Hara H. Suzuki K. Tetrahedron Lett.  1989,  30:  5443 
• 6i Shimazaki M. Morimoto M. Suzuki K. Tetrahedron Lett.  1990,  31:  3335 
• 6j Nagasawa T. Taya K. Kitamura M. Suzuki K. J. Am. Chem. Soc.  1996,  118:  8949 
• For recent studies from other laboratories, see:
• 7a Marson CM. Walker AJ. Pickering J. Hobson AD. Wrigglesworth R. Edge SJ. J. Org. Chem.  1993,  58:  5944 
• 7b Jung ME. D’Amico DC. J. Am. Chem. Soc.  1995,  117:  7379 
• 7c Jung ME. Marquez R. Org. Lett.  2000,  2:  1669 
• 7d Fan C.-A. Wang B.-M. Tu Y.-Q. Song Z.-L. Angew. Chem. Int. Ed.  2001,  40:  3877 
• 8a Eom KD. Raman JV. Kim H. Cha JK. J. Am. Chem. Soc.  2003,  125:  5415 
• 8b Epstein OL. Cha JK. Angew. Chem. Int. Ed.  2005,  44:  121 
• 9 Cho SY. Lee JC. Cha JK. J. Org. Chem.  1999,  64:  3394 
• 10a Allain EJ. Hager LP. Deng L. Jacobsen EN.
  J. Am. Chem. Soc.  1993,  115:  4415 
• 10b Jacobsen EN. In Catalytic Asymmetric Synthesis   Ojima I. VCH; Weinheim: 1993.  Chap. 4.2.
• 10c Annis DA. Jacobsen EN. J. Am. Chem. Soc.  1999,  121:  4147 
• 11 Wang Z.-X. Tu Y. Frohn M. Zhang J.-R. Shi Y. J. Am. Chem. Soc.  1997,  119:  11224 
• 12 For a review, see: Aggarwal VK. Ali A. Coogan MP. Tetrahedron  1999,  55:  293 
• For selected syntheses of nonracemic norcamphor or norbornenone derivatives, see:
• 13a Paquette LA. Doecke CW. Kearney FR. Drake AF. Mason SF. J. Am. Chem. Soc.  1980,  102:  7228 
• 13b Corey EJ. Loh T.-P. J. Am. Chem. Soc.  1991,  113:  8966 
• 13c Ishihara K. Gao Q. Yamamoto H. J. Org. Chem.  1993,  58:  6917 
• 13d Aggarwal VK. Anderson ES. Elfyn JD. Obierey KB. Giles R. Chem. Commun.  1998,  1985 
• 13e See also: Ishihara K. Nakano K. J. Am. Chem. Soc.  2007,  129:  8930 

14

Tin(IV) chloride had successfully been employed for a stereoselective, semipinacol rearrangement of 2,3-epoxy alcohols without protection of alcohols.^7a

15

As 12 was found to be somewhat labile toward acid (e.g., SiO₂), it was isolated as the corresponding E-enone.