One-Pot Synthesis of Functionalized Carbacycles by Formal [3+3] Cyclizations of 1,3-Bis(silyl enol ethers) with 1,3-Dielectrophiles

Abstract

Lewis acid mediated [3+3] cyclizations of 1,3-bis(silyl enol ethers) with 1,3-dielectrophiles, such as 1,1,3,3-tetramethoxy­propane, 3-silyloxy-2-en-1-ones and 1,1-diacylcyclopropanes, provide an efficient approach to a variety of functionalized arenes (such as salicylates and phenols) and other six-membered carbacyclic products.

• 1 Introduction

• 2 [3+3] Cyclizations of 1,3-Bis(silyl enol ethers) with 1,3-Bis(acetals)

• 3 [3+3] Cyclizations of 1,3-Bis(silyl enol ethers) with 1,3-Ketoacetals and 1,3-Keto-S,O-acetals

• 4 [3+3] Cyclizations of 1,3-Bis(silyl enol ethers) with 3-Alkoxy-2-en-1-ones and 3-Silyloxy-2-en-1-ones

• 4.1 Preparative Scope

• 4.2 Synthetic Applications

• 5 [3+3] Cyclizations of 1,3-Bis(silyl enol ethers) with 1,1-Diacylcyclopropanes

• 6 [3+3] Cyclizations of 1,3-Bis(silyl enol ethers) with 1,1-Diacylcyclopentanes

• 7 [3+3] Cyclizations of 1,3-Bis(silyl enol ethers) with 3-Oxoalkanoic acid derivatives

• 8 [3+3] Cyclizations of 1-Silyloxy-1-alkoxy-3-arylthiobuta-1,3-dienes, 1,3-Dialkoxy-1-silyloxybuta-1,3-dienes and 1-Silyloxy-1-alkoxy-3-aryloxybuta-1,3-dienes

• 9 Conclusions

Key words

arenes - cyclization - one-pot reaction - salicylic acid - silyl enol ethers

References

• For reviews of domino reactions, see:
• 1a Tietze LF. Beifuss U. Angew. Chem., Int. Ed. Engl.  1993,  32:  131 ; Angew. Chem. 1993, 105, 137
• 1b Tietze LF. Chem. Rev.  1996,  96:  115 
• For reviews of the application of dianions as building blocks in one-pot cyclizations, see:
• 1c Langer P. Freiberg W. Chem. Rev.  2004,  104:  4125 
• 1d Langer P. Döring M. Eur. J. Org. Chem.  2002,  221 
• 1e Langer P. Chem. Eur. J.  2001,  7:  3858 
• For a review of biomimetic syntheses of polyhydroxylated aromatic compounds based on reactions of 1,3-dicarbonyl dianions, see:
• 1f Harris TM. Harris CM. Tetrahedron  1977,  33:  2159 
• Reviews:
• 2a Brownbridge P. Synthesis  1983,  1 
• 2b Brownbridge P. Synthesis  1983,  85 
• 2c Rasmussen JK. Synthesis  1977,  91 
• 2d Jørgensen KA. Angew. Chem., Int. Ed. Engl.  2000,  39:  3558 ; Angew. Chem. 2000, 112, 3702
• 2e Danishefsky SJ. Bilodeau MT. Angew. Chem., Int. Ed. Engl.  1996,  35:  1380 ; Angew. Chem. 1996, 108, 1482
• 2f Bednarski MD. Lyssikatos JP. In Comprehensive Organic Synthesis: Selectivity, Strategy and Efficiency in Modern Organic Chemistry   Vol. 2:  Trost BM. Fleming I. Pergamon; Oxford: 1991.  p.661 
• Reviews:
• 3a Langer P. Synthesis  2002,  441 
• 3b Langer P. Synlett  2006,  3369 
• 4 Chan T.-H. Brownbridge P. J. Chem. Soc., Chem. Commun.  1979,  578 
• 6 Chan TH. Stössel D. J. Org. Chem.  1986,  51:  2423 
• 7 Chan TH. Stössel D. J. Org. Chem.  1988,  53:  4901 
• 8 Nguyen VTH. Bellur E. Langer P. Tetrahedron Lett.  2006,  47:  113 
• 9 Nguyen VTH. Langer P. Tetrahedron Lett.  2005,  46:  815 
• 10 Nguyen VTH. Appel B. Langer P. Tetrahedron  2006,  62:  7674 
• 11 Chan T.-H. Brownbridge P. J. Am. Chem. Soc.  1980,  102:  3534 
• 12 Brownbridge P. Chan T.-H. Brook MA. Kang GJ. Can. J. Chem.  1983,  61:  688 
• 13 Nguyen VTH. Bellur E. Appel B. Langer P. Synthesis  2006,  1103 
• 14 Kang GJ. Chan TH. J. Org. Chem.  1985,  50:  452 
• 17 Dede R. Langer P. Tetrahedron Lett.  2004,  45:  9177 
• 18 Reim S. Lubbe M. Langer P. Tetrahedron Lett.  2006,  47:  6751 
• 19 Ahmed Z. Langer P. Tetrahedron Lett.  2006,  47:  417 
• 20 Ahmed Z. Langer P. Synlett  2006,  3361 
• 21 Mamat C. Pundt T. Schmidt A. Langer P. Tetrahedron Lett.  2006,  47:  2183 
• 22 Lubbe M. Mamat C. Langer P. Tetrahedron  2007,  63:  413 
• 23 Nguyen VTH. Langer P. Tetrahedron Lett.  2005,  46:  1013 
• 24 Reim S. Lau M. Langer P. Tetrahedron Lett.  2006,  47:  6903 
• 25 Ahmed Z. Fischer C. Spannenberg A. Langer P. Tetrahedron  2006,  62:  4800 
• 26 Ullah E. Appel B. Fischer C. Langer P. Tetrahedron  2006,  62:  9694 
• 27 Langer P. Bose G. Angew. Chem. Int. Ed.  2003,  42:  4033 ; Angew. Chem. 2003, 115, 4165
• 28 Bose G. Nguyen VTH. Ullah E. Lahiri S. Görls H. Langer P. J. Org. Chem.  2004,  69:  9128 
• 29 Bose G. Langer P. Tetrahedron Lett.  2004,  3861 
• 30 Bose G. Bracht K. Bednarski PJ. Lalk M. Langer P. Bioorg. Med. Chem.  2006,  14:  4694 
• 31 Bose G. Ullah E. Langer P. Chem. Eur. J.  2004,  10:  6015 
• 32 Chan TH. Chaly T. Tetrahedron Lett.  1982,  23:  2935 
• 33 Chan TH. Prasad CVC. J. Org. Chem.  1986,  51:  3012 
• 34 Mroß G. Langer P. Tetrahedron Lett.  2006,  47:  8519 

5

Ahmed, Z.; Büttner, S.; Sher, M.; Trabhardt, T.; Langer, P. unpublished results.

15

Höttecke, N.; Fischer, C.; Reinke, H.; Langer, P. unpublished results.

16

Reim, S.; Langer, P. unpublished results.