Abstract
A variety of oxime mesitylenesulfonates, generated in situ from their heterocyclic, carbocyclic, and acyclic ketoximes in the presence of lithium hydroxide in tetrahydrofuran, efficiently rearrange into their corresponding lactams and amides. The stereochemistry of diazepan-5-one lactams resulting from the rearrangement of heterocyclic ketoximes (piperidin-4-one oximes), has been deduced based on one- and two-dimensional NMR analyses. The seven-membered heterocyclic ring of the product lactams adopts chair conformations with equatorial configurations of all the alkyl and aryl substituents except one of the methyl groups at C-3 on a 3,3-disubstituted product, which possess an axial configuration.
Key words
piperidin-4-one oximes - ketoximes - mesitylenesulfonyl chloride - Beckmann rearrangement - diazepan-5-ones - lactams - amides
References
1a Gawley RE.
Org. React.
1988,
35:
1
1b Donaruma LG.
Heldt WZ.
Org. React.
1960,
11:
1
2 Arisawa M.
Yamaguchi M.
Org. Lett.
2001,
3:
311
3a De Luca L.
Giacomelli G.
Porcheddu A.
J. Org. Chem.
2002,
67:
6272
3b Furuya Y.
Ishihara K.
Yamamoto H.
J. Am. Chem. Soc.
2005,
127:
11240
4a Chandrasekhar S.
Gopalaiah K.
Tetrahedron Lett.
2002,
43:
2455
4b Dongare MK.
Bhagwat VV.
Ramana CV.
Gurjar MK.
Tetrahedron Lett.
2004,
45:
4759
4c Wang B.
Gu Y.
Luo C.
Yang T.
Yang L.
Suo L.
Tetrahedron Lett.
2004,
45:
3369
4d Li D.
Shi F.
Guo S.
Deng Y.
Tetrahedron Lett.
2005,
46:
671
4e Kusama H.
Yamashita Y.
Narasaka K.
Bull. Chem. Soc. Jpn.
1995,
68:
373
4f Narasaka K.
Kitamura M.
Eur. J. Org. Chem.
2005,
4505 ; and references cited therein
5a Ikushima Y.
Hatakeda K.
Sato O.
Yokoyama T.
Arai M.
Angew. Chem. Int. Ed.
1999,
38:
2910
5b Ikushima Y.
Hatakeda K.
Sato M.
Sato O.
Arai M.
Chem. Commun.
2002,
19:
2208
5c Boero M.
Ikeshoji T.
Liew CC.
Terakura K.
Parrinello M.
J. Am. Chem. Soc.
2004,
126:
6280
6a Guo S.
Deng Y.
Catal. Commun.
2005,
6:
225
6b Guo S.
Du Z.
Zhang S.
Li D.
Li Z.
Deng Y.
Green Chem.
2006,
8:
296
7a Forni L.
Fornasari G.
Giordano G.
Lucarelli C.
Katovic A.
Trifiro F.
Perri C.
Nagy JB.
Phys. Chem. Chem. Phys.
2004,
6:
1842
7b Ghiaci M.
Abbaspur A.
Kalbasi R.
Appl. Catal., A
2005,
287:
83
8 Ramalingan C.
Park Y.-T.
J. Org. Chem.
2007,
72:
4536
9a Kelly TA.
McNeil DW.
Rose JM.
David E.
Shih CK.
Grob PM.
J. Med. Chem.
1997,
40:
2430
9b Tucker H.
Le Count DJ.
Comprehensive Heterocyclic Chemistry II
Vol. 9:
Newkome GR.
Elsevier;
Oxford:
1996.
p.151 and 1039
9c Thurston DE.
Molecular Aspects of Anticancer Drug-DNA Interactions
The Macmillan Press Ltd.;
London:
1993.
p.54
9d Thurston DE.
Bose DS.
Chem. Rev.
1994,
94:
433
10 Ramalingan C.
Park Y.-T.
Kabilan S.
Eur. J. Med. Chem.
2006,
41:
683 ; and references cited therein
11 The E -oxime 1a adopts classical chair-conformation with equatorial orientations of the phenyl groups on C-2 and C-6, and the methyl group on C-3. Key evidence for the orientation of the hydroxyl group of the oxime being anti (E ) to C-3 is the unusual downfield absorption of the equatorial proton on C-5 compared to the absorptions of the protons on C-2 and C-6 in the 1 H NMR spectrum, due to the 1,3-spatial proximity effect between the equatorial proton on C-5 and the oxygen of the oxime (Refer to references 10 and 12 for more details).
12 Cope AC.
Cotter RJ.
Roller GG.
J. Am. Chem. Soc.
1955,
77:
3590
13a Abraham RJ.
Fisher J.
Loftus P.
Introduction to NMR Spectroscopy
John Wiley;
New York:
1988.
p.45
13b Cooper JW.
Spectroscopic Techniques for Organic Chemists
John Wiley;
New York:
1980.
p.45
14a Katritzky AR.
Advances in Heterocyclic Chemistry
Vol. 36:
Academic Press;
New York:
1984.
p.42
14b Trager WF.
Lee CM.
Beckett AH.
Tetrahedron
1967,
23:
365
14c Wiewiorowski M.
Skolik J.
Krueger PJ.
Tetrahedron
1968,
24:
5439
15 Tamura Y.
Fujiwara H.
Sumoto K.
Ikeda M.
Kita Y.
Synthesis
1973,
215
16 Cristau HJ.
Cellier PP.
Spindler JF.
Taillefer M.
Chem. Eur. J.
2004,
10:
5607
17 Young CG.
Pauline R.
Jenny J.
Christian M.
Carsten B.
Org. Lett.
2004,
6:
3293
18 Chretien JM.
Zammattio F.
Le Grognec E.
Paris M.
Cahingt B.
Montavon G.
Quintard JP.
J. Org. Chem.
2005,
70:
2870
19 Wan X.
Ma Z.
Li B.
Zhang K.
Cao S.
Zhang S.
Shi Z.
J. Am. Chem. Soc.
2006,
128:
7416
20 Larock RC.
Yum EK.
Refvik MD.
J. Org. Chem.
1998,
63:
7652
21
1 H NMR spectra were compared to those obtained from corresponding authentic samples.
22 Matallana A.
Kruger AW.
Kingsbury CA.
J. Org. Chem.
1994,
59:
3020
