New Samarium Diiodide-Induced Ketyl Couplings - From Analogous Reactions to Serendipitously Discovered Processes

Abstract

Analogous applications of samarium diiodide as a promoter for ketyl cyclizations led to the discovery of several new and synthetically interesting reactions. Whereas samarium ketyl cyclizations with alkyne and allene units could be expected - though they have not been known before - the unplanned cyclization of the ketyl towards an aromatic ring uncovered a new mode of reaction. The resulting hexahydronaphthalene derivatives were formed in excellent diastereoselectivities and are synthetically very valuable building blocks. This new method was systematically investigated and extended to polycyclic compounds and those with heteroatoms in the spacer between the carbonyl group and the aromatic ring. The cyclizations involving indole and pyrrole derivatives are most promising for the stereoselective construction of alkaloid skeletons.

1 Introduction

2 Reductive Cyclizations of Alkenes to Benzannulated Cyclooctane Derivatives

3 Reductive Cyclizations of Alkynes to Cyclooctene Derivatives

4 Reactions of Allene Derivatives

5 A Novel Cyclization of Samarium Ketyls - Involvement of Aryl Substituents and Formation of Hexahydronaphthalene Derivatives

6 Stereoselective Synthesis of Tricyclic and Tetracyclic Compounds by Reductive Cyclizations of Naphthalene Derivatives

7 Reductive Cyclizations of α- and β-Aminoketones to Isoquinoline and Quinoline Derivatives

8 Reductive Cyclizations of Indole and Pyrrole Derivatives

9 Conclusion

Key words

samarium diiodide - electron transfer - ketyl - carbocycles - heterocycles - steroids - indole - alkynes - allenes

References

• 1a Mehta G. Singh V. Chem. Rev.  1999,  99:  881 
• 1b Petasis NA. Patane MA. Tetrahedron  1992,  48:  5757 
• 2 Nicolaou KC. Dai WM. Guy RK. Angew. Chem., Int. Ed. Engl.  1994,  33:  15 ; Angew. Chem. 1994, 106, 38
• 3 Reissig H.-U. Zimmer R. Chem. Rev.  2003,  103:  1151 
• 4a Khan FA. Czerwonka R. Reissig H.-U. Synlett  1996,  533 
• 4b Khan FA. Czerwonka R. Reissig H.-U. Eur. J. Org. Chem.  2000,  3607 
• 5a Girard PG. Namy JL. Kagan HB. Nouv. J. Chim.  1977,  1:  5 
• 5b Girard PG. Namy JL. Kagan HB. J. Am. Chem. Soc.  1980,  102:  2693 
• 6a Molander GA. Chem. Rev.  1992,  92:  29 
• 6b Molander GA. Harris CR. Chem. Rev.  1996,  96:  307 
• 6c Molander GA. Harris CR. Tetrahedron  1998,  54:  3321 
• 6d Khan FA. Zimmer R. J. Prakt. Chem.  1997,  339:  101 
• 6e Krief A. Laval A.-M. Chem. Rev.  1999,  99:  745 
• 6f Steel PG. J. Chem. Soc., Perkin Trans. 1  2001,  2727 
• 6g Hölemann A. Synlett  2001,  1497 
• 7a Molander GA. McKie JA. J. Org. Chem.  1992,  57:  3132 
• 7b Molander GA. Acc. Chem. Res.  1998,  31:  603 
• 7c Monovich LG. Le Huérou Y. Rönn M. Molander GA. J. Am. Chem. Soc.  2000,  122:  52 
• 7d Molander GA. George KM. Monovich LG. J. Org. Chem.  2003,  68:  9533 
• 8 Khan FA. Czerwonka R. Zimmer R. Reissig H.-U. Synlett  1997,  995 
• 9 Zimmer R. Zahn G. Khan FA. Reissig H.-U. Acta Crystallogr., Sect. C  1999,  55:  1941 
• 11a Otsububo K. Inanaga J. Yamaguchi M. Tetrahedron Lett.  1986,  27:  5763 
• 11b Shabangi M. Flowers RA. Tetrahedron Lett.  1997,  38:  1137 
• 11c Shotwell JB. Sealy JM. Flowers RA. J. Org. Chem.  1999,  64:  5251 
• 11d Prasad E. Flowers RA. J. Am. Chem. Soc.  2002,  124:  6895 
• 11e For a review dealing with effects of solvents and additives see: Kagan HB. Namy JL. Topics in Organometallic Chemistry  1999,  2:  155 
• 14 Rademacher O. Zimmer R. Dinesh CU. Reissig H.-U. Z. Kristallogr. NCS  2002,  217:  423 
• 15 Nandanan E. Dinesh CU. Reissig H.-U. Tetrahedron  2000,  56:  4267 
• 16 Lentz D. Nandanan E. Reissig H.-U. Z. Kristallogr. NCS  2001,  216:  525 
• 18 For related reductive fragmentations see: Haque A. Gosh S. Chem. Commun.  1997,  2039 
• 19 Curran DP. Fevig TL. Jasperse CP. Totleben MJ. Synlett  1992,  943 
• 21 Hölemann A. Reissig H.-U. Org. Lett.  2003,  5:  1463 
• 22 Dinesh CU. Reissig H.-U. Angew. Chem. Int. Ed.  1999,  38:  789 ; Angew. Chem. 1999, 111, 874
• 23a Shiue J.-S. Lin C.-C. Fang JM. Tetrahedron Lett.  1993,  34:  335 
• 23b Shiue J.-S. Lin M.-H. Fang JM. J. Org. Chem.  1997,  62:  4643 
• 24a Rabideau PW. Marcinow Z. Org. React.  1992,  42:  1 
• 24b Birch AJ. Pure Appl. Chem.  1996,  68:  553 
• 25a Pape AR. Kaliappan KP. Kündig EP. Chem. Rev.  2000,  100:  2917 
• 25b Harmann WD. Chem. Rev.  1997,  97:  1953 
• 25c For a comprehensive compilation of important reviews and recent original references see: Fernández I. Forcén-Acebal A. García-Granda S. López-Ortiz F. J. Org. Chem.  2003,  68:  4472 
• 26a Shono T. Kise N. Suzumoto T. Morimoto T. J. Am. Chem. Soc.  1986,  108:  4676 
• 26b Kise N. Suzumoto T. Shono T. J. Org. Chem.  1994,  59:  1407 
• 27a Gorny R. Schäfer HJ. Fröhlich R. Angew. Chem., Int. Ed. Engl.  1995,  34:  2007 ; Angew. Chem. 1995, 107, 2188
• 27b Heimann J. Schäfer HJ. Fröhlich R. Wibbeling B. Eur. J. Org. Chem.  2003,  2919 
• 28a Schmalz H.-G. Siegel S. Bats JW. Angew. Chem., Int. Ed. Engl.  1995,  34:  2383 ; Angew. Chem. 1995, 107, 2597
• 28b Schellhaas K. Schmalz HG. Bats JW. Chem. Eur. J.  1998,  4:  57 
• 28c Schmalz H.-G. Kiehl O. Battsengel G. Synlett  2002,  1253 
• 29 Berndt M. Dissertation   Freie Universität Berlin; Germany: 2003. 
• 30 Taylor EC. Wang Y. Heterocycles  1998,  48:  1537 
• 31 Berndt M. Reissig H.-U. Synlett  2001,  1290 
• 32 Rademacher O. Berndt M. Reissig H.-U. Z. Kristallogr. NCS  2001,  216:  593 
• 33a Ohno H. Maeda S.-L. Okumura M. Wakayama R. Tanaka T. Chem. Commun.  2002,  316 
• 33b Ohno H. Okumura M. Maeda S.-L. Iwasaki H. Wakayama R. Tanaka T. J. Org. Chem.  2003,  68:  7722 
• 34 Ohno H. Wakayama R. Maeda S. Iwasaki H. Okumura M. Iwata C. Mikamiyama H. Tanaka T. J. Org. Chem.  2003,  68:  5909 
• 35 Dinesh CU. Reissig H.-U. Rademacher O. Z. Kristallogr. NCS  2000,  215:  615 
• 37 Kuo C.-W. Fang JM. Synth. Commun.  2001,  31:  877 
• 38 Gross S. Dissertation   Freie Universität Berlin; Germany: 2003. 
• 40 Gross S. Reissig H.-U. Synlett  2002,  2027 
• 41a List B. Pojarliev P. Biller WT. Martin HJ. J. Am. Chem. Soc.  2002,  124:  827 
• 41b Cordova A. Notz W. Zhong G. Betancort JM. Barbas CF. J. Am. Chem. Soc.  2002,  124:  1842 
• 44 Gross S. Reissig H.-U. Org. Lett.  2003,  5:  4305 
• 45 Lin S.-C. Yang F.-D. Shiue J.-S. Yang S.-M. Fang JM. J. Org. Chem.  1998,  63:  2909 

10

Zimmer, R.; Reissig, H.-U. unpublished results.

12

Several substitutes have been tested (see ref. 11b), however only recently we found that phosphoric acid derivatives which are probably not carcinogenic may be equivalent to HMPA in many samarium diiodide-induced reactions (ref. 29), Berndt, M.; Reissig, H.-U. to be submitted.

13

Khan, F. A.; Dinesh, C. U.; Reissig, H.-U. unpublished results.

17

Dinesh, C. U.; Nandanan, E.; Reissig, H.-U. unpublished results.

20

Hölemann, A. Dissertation; Freie Universität Berlin: Germany, 2004.

36

Hlobilova, I.; Reissig, H.-U. unpublished results.

39

X-ray data for 134 submitted: Brüdgam, I.; Gross, S.; Hartl, H.; Reissig, H.-U. Z. Kristallogr. NCS.

42

X-ray data for 155 submitted: Brüdgam, I.; Gross, S.; Hartl, H.; Reissig, H.-U. Z. Kristallogr. NCS.

43

The enantiopurity of compounds 154-156 and their precursors has so far not been checked since we were primarily interested whether the cyclization occurs or not.