(
1 mmol) was added in one portion. After a further 25 minutes,
8 For reports on oxazolidin-2-one-derived N-carbinols see: (a) J. Bach,
S. D. Bull, S. G. Davies, R. L. Nicholson, H. J. Sanganee and A. D.
Smith, Tetrahedron Lett., 1999, 40, 6677; (b) S. D. Bull, S. G. Davies,
R. L. Nicholson, H. J. Sanganee and A. D. Smith, Tetrahedron:
Asymmetry, 2000, 11, 3475; (c) J. Bach, C. Blachere, S. D. Bull, S. G.
Davies, R. L. Nicholson, P. D. Price, H. J. Sanganee and A. D. Smith,
Org. Biomol. Chem., 2003, 1, 2001; (d) S. G. Davies, I. A. Hunter, R. L.
Nicholson, P. M. Roberts, E. D. Savory and A. D. Smith, Tetrahedron,
◦
the reaction was cooled to −78 C and isobutyraldehyde (0.09 mL,
1
mmol) was added. After a further 30 minutes, the reaction was
◦
quenched by the addition of a pre-cooled (−78 C) solution of
acetic acid (1.5 mL, 1.5 mmol, 1.0 M in THF). After a further
◦
3
1
2
0 minutes, the reaction was allowed to warm to 0 C over
5 minutes before being filtered though a plug of silica (25 mm × ø
5 mm) eluting with ethyl acetate and concentrated under reduced
2
004, 60, 7553; (e) S. G. Davies, R. L. Nicholson and A. D. Smith, Org.
Biomol. Chem., 2005, 3, 348; (f) C. Gaul and D. Seebach, Org. Lett.,
000, 2, 1501; (g) C. Gaul, K. Scharer and D. Seebach, J. Org. Chem.,
2001, 66, 3059; (h) C. Gaul and D. Seebach, Helv. Chim. Acta, 2002,
5, 772.
A. H. Hoveyda, D. A. Evans and G. C. Fu, Chem. Rev., 1993, 93, 1307.
2
pressure to give the crude product. The yield and enantiomeric
excess were determined by H NMR with DCM as an internal
standard and chiral HPLC respectively. All spectroscopic data
were consistent with those previously recorded.
1
8
9
10 The one-pot enantioselective synthesis of aldehydes via addition of
chiral lithium amides followed by ortho-lithiation or directed organo-
lithium addition has been reported: (a) A. Alexakis, T. Kanger, P.
Mangeney, F. Rosemunch, A. Perrotey and E. Rose, Tetrahedron:
Asymmetry, 1995, 6, 2135; (b) A. Alexakis, T. Kanger, P. Mangeney, F.
Rosemunch, A. Perrotey and E. Rose, Tetrahedron: Asymmetry, 1995, 6,
47; (c) G. G. A. Balavoine, J. C. Daran, G. Iftime, E. Manoury and C. J.
Moreau-Bossuet, J. Organomet. Chem., 1998, 567, 191; (d) G. Iftime,
J. C. Daran, E. Manoury and G. G. A. Balavoine, Angew. Chem., Int.
Ed., 1998, 37, 1698; (e) N. Br e´ mand, P. Mangeney and J. F. Normant,
Tetrahedron Lett., 2001, 42, 1883.
11 A similar approach using a reversible diastereoselective aldol addition
has recently been reported: M. Cheeseman, F. J. P. Feuillet, A. L.
Johnson and S. D. Bull, Chem. Commun., 2005, 2374.
2 (a) K. C. Nicolaou and E. J. Sorensen, Classics in total synthesis: targets,
strategies, methods, Wiley-VCH, Weinheim, 1996; (b) K. C. Nicolaou
and S. A. Snyder, Classics in total synthesis II: more targets, strategies,
methods, Wiley-VCH, Weinheim, 2003.
General procedure four—Table 10, entries d–f and j–m
Base (0.2 mmol) was added to a stirred solution of pyrrole
(
was allowed to warm to room temperature over 5 minutes before
the ligand (0.4 mmol) was added in one portion. After a further
◦
0.150 mL, 2.0 mmol) in toluene (10 mL) at 0 C. The solution
◦
2
5 minutes, the reaction was cooled to −78 C and aldehyde
(
1.0 mmol) was added dropwise over 1 minute. After 30 minutes,
the reaction was quenched by the addition of a pre-cooled
(
After a further 30 minutes, the reaction was allowed to warm to
0
◦
−78 C) solution of acetic acid (1.0 mL, 1.0 mmol, 1.0 M in THF).
1
1
◦
C over 15 minutes before being filtered though a plug of silica
(
25 mm × ø 25 mm) eluting with ethyl acetate and concentrated
3 (a) S. Matsunaga, T. Kinoshita, S. Okada, S. Harada and M. Shibasaki,
J. Am. Chem. Soc., 2004, 126, 7559; (b) S. Harada, S. Handa, S.
Matsunaga and M. Shibasaki, Angew. Chem., Int. Ed., 2005, 44,
under reduced pressure to give the crude product. The yield and
enantiomeric excess were determined by H NMR with DCM as an
internal standard and chiral HPLC respectively. All spectroscopic
data were consistent with those previously recorded.
1
4
365.
4 R. D. Richardson, F. A. Hernandez Juan and D. J. Dixon, Synlett,
006, 77.
1
1
1
2
5 A. Thompson, E. G. Corley, M. F. Huntington, E. J. J. Grabowski, J. F.
Remenar and D. B. Collum, J. Am. Chem. Soc., 1998, 120, 2028.
6 (1R,2S)-2-Pyrrolidine-1-phenylpropan-1-ol was kindly donated by
Dr J. W. Burton: D. Zhao, C. Chen, F. Xu, L. Tan, R. Tillyer, M. E.
Pierce and J. R. Moore, Org. Synth., 1999, 77, 12.
7 M. A. Beswick and D. S. Wright, in Comprehensive Organometallic
Chemistry II, ed. E. W. Abel, F. G. A. Stone and G. Wilkinson,
Pergmamon Press, Oxford, 1995, ch. 1.
Acknowledgements
We gratefully acknowledge the financial support of As-
traZeneca/EPSRC for a studentship (to M.S.S.), GSK/EPSRC
for a studentship (to A.C.L.). We thank EPSRC National Mass
Spectrometry Service Centre, Swansea, for analysis.
1
1
1
8 (a) G. R. Sullivan, J. A. Dale and H. S. Mosher, J. Org. Chem., 1973, 38,
2
143, for a recent review see: (b) J. M. Seco, E. Qui n˜ o a´ and R. Riguera,
Chem. Rev., 2004, 104, 17.
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326 | Org. Biomol. Chem., 2006, 4, 1313–1327
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