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DOI: 10.1055/s-2004-815429
New Samarium Diiodide-Induced Ketyl Couplings - From Analogous Reactions to Serendipitously Discovered Processes
Publication History
Publication Date:
26 January 2004 (online)
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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
-
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
References
Zimmer, R.; Reissig, H.-U. unpublished results.
12Several 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.
13Khan, F. A.; Dinesh, C. U.; Reissig, H.-U. unpublished results.
17Dinesh, C. U.; Nandanan, E.; Reissig, H.-U. unpublished results.
20Hölemann, A. Dissertation; Freie Universität Berlin: Germany, 2004.
36Hlobilova, I.; Reissig, H.-U. unpublished results.
39X-ray data for 134 submitted: Brüdgam, I.; Gross, S.; Hartl, H.; Reissig, H.-U. Z. Kristallogr. NCS.
42X-ray data for 155 submitted: Brüdgam, I.; Gross, S.; Hartl, H.; Reissig, H.-U. Z. Kristallogr. NCS.
43The 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.