COMMUNICATIONS
Table 3. [Pd(PPh3)4]-catalyzed tandem double-addition cyclization of 1a
with PhI and different imines 4 in THF or 1,4-dioxane.[a]
Pinder, Nat. Prod. Rep. 1992, 9, 17; d) G. Massiot, C. Ddelaude in
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amides with aryl or vinyl halides, see: a) S.-K. Kang, K.-J. Kim, Org.
Lett. 2001, 3, 511; b) I. W. Davies, D. I. C. Scopes, T. Gallagher, Synlett
1993, 85.
Entry
R
Solvent[b]
5
Yield of 2a [%]
Yield[%] cis/trans
[11] For the Agþ-catalyzed cycloisomerization of g-allenic amides, see:
a) I. W. Davies, T. Gallagher, R. B. Lamont, D. I. C. Scopes, J. Chem.
Soc. Chem. Commun. 1992, 335; b) D. N. A. Fox, D. Lathbury, M. F.
Mahon, K. C. Molloy, T. Gallagher, J. Chem. Soc. Chem. Commun.
1989, 1073; c) R. Kinsman, D. Lathbury, P. Vernon, T. Gallagher, J.
Chem. Soc. Chem. Commun. 1987, 243; for lanthanide-catalyzed
cycloisomerization of g-allenic amides, see: V. M. Arredondo, S. Tian,
F. E. McDonald, T. J. Marks, J. Am. Chem. Soc. 1999, 121, 3633.
[12] For the Pd-catalyzed two-component reaction of 2-(2,3-allenyl)mal-
onates with electron-deficient alkenes leading to five-membered
carbocycles, see: M. Meguro, Y. Yamamoto, J. Org. Chem. 1999, 64,
694.
1
2
3
4[c]
5
p-O2NC6H4 (4b) THF
p-O2NC6H4 (4b)
p-MeOC6H4 (4c) THF
p-MeOC6H4 (4c) THF
89 (5i)
95 (5i)
52 (5j)
99 (5j)
52 (5j)
95 (5k)
95:5
97:3
> 99:1 42
> 99:1
97:3 29
> 98:2
0
0
A
0
p-MeOC6H4 (4c)
p-ClC6H4 (4d)
A
THF
6
0
[a] PhI (1.2 equiv) was used. [b] A ¼ 1,4-dioxane; [c] Imine 4c (3.0 equiv)
was used.
[13] For the Pd-catalyzed cycloisomerization of allenes with a nucleophilic
center, see: a) S. Kamijo, Y. Yamamoto, Tetrahedron Lett. 1999, 40,
1747; b) M. Meguro, S. Kamijo, Y. Yamamoto, Tetrahedron Lett. 1996,
37, 7453; c) B. M. Trost, P.-Y. Michellys, V. J. Gerusz, Angew. Chem.
1997, 109, 1837; Angew. Chem. Int. Ed. 1997, 36, 1750.
[14] For the Pd-catalyzed coupling cyclization of 2-(2,3-allenyl)malonates
with organohalides, see: a) L. Besson, J. Bazin, J. Gore, B. Cazes,
Tetrahedron Lett. 1994, 35, 2881; b) M. Ahmar, B. Cazes, J. Gore,
Tetrahedron Lett. 1985, 26, 3795; c) S. Ma, S. Zhao, Org. Lett. 2000, 2,
2495; d) S. Ma, N. Jiao, S. Zhao, H. Hou, J. Org. Chem. 2002, 67, 2837.
[15] X-ray data for compound 5a: C29H29NSO6, Mr ¼ 519.61, triclinic, space
group P1 (#2), a ¼ 10.228(2), b ¼ 13.310(4), c ¼ 9.980(2) ä, V¼
1328.9(5) ä3, a ¼ 97.57(2)8, b ¼ 96.13(2)8, g ¼ 96.17(2)8, T¼ 20.08C,
Z ¼ 2, m(MoKa) 1.65 cmÀ1, reflections collected 4926 (unique 4642),
number of data with I > 3.00s(I) 3978, parameters 335, R1 ¼ 0.043,
Rw ¼ 0.057, Rint ¼ 0.022. CCDC-189277 contains the supplementary
crystallographic data for this paper. These data can be obtained free of
Cambridge Crystallographic Data Centre, 12, Union Road, Cam-
bridge CB21EZ, UK; fax: (þ 44)1223-336-033; or deposit@ccdc.cam.
ac.uk).
Scheme 3. Synthesis of 5l from 1b and imine 4a.
1H), 2.60 (dd, J ¼ 13.70, 5.98 Hz, 1H), 2.39 ppm (s, 3H); 13C NMR
(75.4 MHz, CDCl3): d ¼ 170.04, 167.18, 147.84, 143.71, 139.88, 139.05,
139.04, 135.69, 129.34, 128.55, 128.51, 128.46, 128.38, 128.25, 128.08,
116.63, 68.14, 64.03, 63.83, 53.73, 52.62, 39.28, 21.79 ppm; MS (70 eV): m/
z (%): 520 (14.32) [MþH]þ, 364 (100); IR (KBr): n˜ ¼ 1749, 1729, 1635, 1597,
1493, 1350, 1165 cmÀ1; elemental analysis: calcd for C29H29NO6S (%):
C 67.03, H 5.63, N 2.70; found C 67.04, H 5.48, N 2.63.
Received: July 9, 2002
Revised: September 10, 2002 [Z19689]
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Catalytic Electronic Activation: Indirect
™Wittig∫ Reaction of Alcohols**
Michael G. Edwards and Jonathan M. J. Williams*
Tandem, domino, and cascade reactions have become
increasingly popular in recent years, driven by the opportunity
to simplify linear sequences and achieve otherwise unfeasible
reactions.[1] Contributions from this group have involved the
idea of ™catalytic electronic activation∫, which temporarily
enhances the electronic nature of a functional group to a given
reaction. We have recently reported the indirect addition of
[*] Prof. Dr. J. M. J. Williams, M. G. Edwards
Department of Chemistry
University of Bath
[6] a) B. M. Trost, Science 1991, 254, 1471; b) B. M. Trost, Angew. Chem.
1995, 107, 285; Angew. Chem. Int. Ed. Engl. 1995, 34, 259.
[7] a) L. F. Tietze, Chem. Rev. 1996, 96, 115; b) P. J. Parsons, C. S. Penkett,
A. J. Shell, Chem. Rev. 1996, 96, 195; c) R. A. Bunce, Tetrahedron
1995, 51, 13103.
Claverton Down, Bath BA2 7AY (UK)
Fax : (þ 44)1225-826-231
E-mail: j.m.j.williams@bath.ac.uk
[**] This work was supported by the EPSRC (M.G.E.).
[8] For some reviews, see: a) D. Enders, C. Thiebes, Pure. Appl. Chem.
2001, 73, 573; b) D. O’hagan, Nat. Prod. Rep. 2000, 17, 435; c) A. R.
Supporting information for this article is available on the WWW under
4740
¹ 2002 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
0044-8249/02/4124-4740 $ 20.00+.50/0
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