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

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 

10

Zimmer, R.; Reissig, H.-U. unpublished results.

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 

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.

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 

17

Dinesh, C. U.; Nandanan, E.; Reissig, H.-U. unpublished results.

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 

20

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

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 

36

Hlobilova, I.; Reissig, H.-U. unpublished results.

37 Kuo C.-W. Fang JM. Synth. Commun.  2001,  31:  877 

38 Gross S. Dissertation   Freie Universität Berlin; Germany: 2003. 

39

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

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 

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.

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