Markus Grohmann et al.
FULL PAPERS
Action D24 “Sustainable Chemical Processes: Stereoselective
Transition Metal-Catalyzed Reactions” is kindly acknowl-
edged.
3-Benzyl-3-azabicyclo
(19)
ACHTRE[UGN 5.3.0]deca-5,7,9-trien-2-one
Obtained from 3d (526 mg, 2.0 mmol) and Rh2ACHTRE(UNG OAc)4
(26.0 mg, 58.8 mmol) as a white powder; yield: 348 mg
1
(74%); mp 1298C; H NMR: d=3.16 (broad s, 1H, 1-H),
2
References
4.06 and 4.07 (AB system, 2H, j Jj=17.2 Hz, 4-H2), 4.56
2
and 4.60 (AB system, 2H, j Jj=14.7 Hz, NCH2), 5.33 (dd,
3
[1] M. P. Doyle, M. A. McKervey, T. Ye, in: Modern Cata-
lytic Methods for Organic Synthesis with Diazo Com-
pounds, John Wiley & Sons, New York, 1998.
[2] A. Padwa, K. E. Krumpe, Tetrahedron 1992, 48, 5385–
5453.
1H, J=9.3 and 3.8 Hz, 10-H), 6.09 (s, 1H, 6-H), 6.17–6.22
(m, 1H, 9-H), 6.45–6.51 (m, 2H, 7-H, 8-H), 7.27–7.32 (m, 5
HPh); 13C NMR: d=46.3 (C-4), 46.5 (C-1), 50.5 (NCH2),
119.5 (C-6), 120.6 (C-10), 125.8 (C-5), 127.0 (C-9), 127.8,
128.2, 129.2, 129.9 (C-7), 130.3 (C-8), 174.0 (CO); IR (KBr):
n=3062, 3029, 2924, 2849 (all m), 1682 (s, CO), 1650 (s),
1475/1455/1442/1425 cmꢀ1 (all m); anal. calcd. for C16H15NO
(237.12): C 80.98, H 6.37, N 5.90; found: C 80.90, H 6.43, N
5.89; MS (100 eV): m/z=238 (100%).
[3] M. P. Doyle, D. C. Forbes, Chem. Rev. 1998, 98, 911–
935.
[4] A. Pfaltz, in: Comprehensive Asymmetric Catalysis,
Vol. 2 (Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto),
Springer-Verlag, New York, 1999, pp. 513–538.
[5] H. M. L. Davies, R. E. Beckwith, Chem. Rev. 2003, 103,
2861–2903.
Rh2ACHTREUNG(OAc)4-Catalyzed Reaction of 3e
The reaction was carried out as described in the general pro-
cedure with 3e (441 mg, 2.0 mmol) and Rh2A(OAc)4 (26.2 mg,
[6] a) A. Bryskier (Ed.), Antimicrobial Agents: Antibacteri-
als and Antifungals, Am. Soc. Microbiology, Washing-
ton DC, 2005; b) b-lactams: B. K. Banik (Ed.), Curr.
Med. Chem. 2004, 11, issue 14; G. S. Singh, Tetrahedron
2003, 59, 7631–7649; M. Sunagawa, A. Sasaki, Hetero-
cycles 2001, 54, 497–528; M. J. Miller (Ed.), Tetrahe-
dron 2000, 56, issue 31; M. I. Page (Ed.), The Chemistry
of b-Lactams, Blackie, Glasgow, UK, 1993; c) g-lac-
tams: X. Z. Zhu, X.-Y. Li, J. Liu, Eur. J. Pharmacology
2004, 500, 221–230; R. Shiraki, K.-I. Tadano, Rev. Het-
eroatom Chem. 1999, 20, 283–307; J. E. Baldwin, G. P.
Lynch, J. Pitlik, J. Antibiotics 1991, 44, 1–24.
[7] G. Maas, Topics Curr. Chem. 1987, 137, 75–253.
[8] P. M. P. Gois, C. A. M. Afonso, Eur. J. Org. Chem.
2004, 3773–3785.
[9] Recent work on Rh-catalyzed carbenoid lactam synthe-
sis: a) A. G. H. Wee, S. C. Duncan, G. Fan, Tetrahe-
dron: Asymmetry 2006, 17, 297–307; b) Z. Chen, Z.
Chen, Y. Jiang, W. Hu, Tetrahedron 2005, 61, 1579–
1586; c) W.-J. Liu, Z.-L. Chen, Z.-Y. Chen, W.-H. Hu,
Tetrahedron: Asymmetry 2005, 16, 1693–1698;
d) P. M. P. Gois, N. R. Candeias, C. A. M. Afonso, J.
Mol. Cat. A 2005, 227, 17–24; e) D. Muroni, A. Saba,
ARKIVOC 2005 (xiii), 1–7; f) D. L. Flanigan, C. H.
Yoon, K. W. Jung, Tetrahedron Lett. 2005, 46, 143–146;
g) Z.-L. Chen, Z.-Y. Chen, Y.-H. Jiang, W. Hu, Synthe-
sis 2004, 1763–1764; h) M. P. Doyle, W. Hu, A. G. H.
Wee, Z. Wang, S. C. Duncan, Org. Lett. 2003, 5, 407–
410; i) C. H. Yoon, A. Niagle, C. Chen, D. Gandhi,
K. W. Jung, Org. Lett. 2003, 5, 2259–2262.
CTHREUNG
59.3 mmol). Column chromatography over basic alumina
[85 g, elution with cyclohexane/ethyl acetate (7:3)] furnished
a) 3-isopropyl-3-azabicycloACHTREU[NG 5.3.0]deca-5,7,9-trien-2-one (23)
(yield: 160 mg, 42%); b) 1-benzyl-4,4-dimethylazetidin-2-
one (22) (52 mg, 13%); c) 1-benzyl-4-methyl-pyrrolidin-2-
one (21) (yield: 137 mg, 36%).
1
3
21:[38] Colorless oil; H NMR: d=1.15 (d, 6H, J=6.3 Hz,
CH3), 1.58–1.62 (m, 1H, 4-H1), 2.14–2.16 (m, 1H, 4-H2),
2.39–2.50 (m, 2H, 3-H2), 3.54 (sext, 1H, 5-H), 3.98 (d, 1H,
2J=15.1 Hz, NCHA), 4.96 (d, 1H, J=14.9 Hz, NCHB), 7.22–
2
7.32 (m, 5 HPh); 13C NMR: d=19.6 (CH3), 26.6 (C-4), 30.2
(C-3), 43.9 (C-5), 52.8 (NCH2), 127.3, 127.9, 128.5, 136.8,
174.9 (CO); IR (KBr): n=1734 (s, CO), 1437 cmꢀ1 (m);
anal. calcd. for C12H15NO (189.25): C 76.16, H 7.99, N 7.40;
found: C 75.83, H 7.97, N 7.56; MS (100 eV): m/z=190
(100%).
1
22:[39] Colorless oil; H NMR: d=1.23 (s, 6H, CH3), 2.76
(s 2H, 3-H2), 4.30 (s, 2H, NCH2), 7.26–7.32 (m, 5 HPh);
13C NMR: d=25.1 (CH3), 43.2 (C-3), 50.6 (NCH2), 56.1 (C-
4), 127.5, 128.3, 128.5, 137.0, 166.3 (CO); IR (KBr): n=2967
(m), 1744 (s, CO), 1391 cmꢀ1 (m); C12H15NO (189.25): calcd.
C 76.16, H 7.99, N 7.40; found: C 76.23, H 8.03, N 7.50; MS
(100 eV): m/z=190 (100%).
23: Colorless oil; 1H NMR: d=1.17 (d, 3H, 3J=6.8 Hz,
CH3), 1.20 (d, 3H, 3J=6.6 Hz, CH3) 3.09 (dd, 1H, J=2.0
and 1.3 Hz, 1-H), 4.17 (s, 2H, 4-H2), 4.51 (sept, 1H, 3J=
6.8 Hz, NCH), 5.28 (dd, 1H, J=3.8 and 9.6 Hz, 10-H), 6.15–
6.19 (m, 2H, 6-H, 9-H), 6.44–6.53 (m, 2H, 7-H, 8-
H);13C NMR: d=19.7 (CH3), 42.5 (CH) 45.8 (C-4), 46.9 (C-
1), 119.4 (C-6), 120.8 (C-10), 126.8 (C-9), 129.7 (C-7), 129.8
(C-8), 130.2 (C-5), 173.2 (CO); IR (KBr): n=2972 (m), 1773
(s, CO), 1473 (m), 1427 cmꢀ1 (m); anal. calcd. for C12H15NO
(189.25): C 76.16, H 7.99, N 7.40; found: C 76.00, H 8.04, N
7.43; MS (100 eV): m/z=190 (100%).
[10] T. Naota, H. Takaya, S.-I. Murahashi, Chem. Rev. 1998,
98, 2599–2660.
[11] B. M. Trost, F. D. Toste, A. B. Pinkerton, Chem. Rev.
2001, 101, 2067–2096.
[12] H. Nishiyama, in: Ruthenium in Organic Synthesis,
(Ed.: S.-I. Murahashi), Wiley-VCH, 2004, chap. 7.
[13] G. Maas, Chem. Soc. Rev. 2004, 183–190.
[14] W.-H. Cheung, S.-L. Zheng, W.-Y. Yu, G.-C. Zhou, C.-
M. Che, Org. Lett. 2003, 5, 2535–2538.
Acknowledgements
[15] S.-L. Zheng, W.-Y. Yu, C.-M. Che, Org. Lett. 2002, 4,
889–892.
This work was supported by the Deutsche Forschungsgemein-
schaft. The support and sponsorship contributed by COST
[16] M. K.-W. Choi, W.-Y. Yu, C.-M. Che, Org. Lett. 2005, 7,
1081–1084.
2210
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2006, 348, 2203 – 2211