Y. Kiyotsuka, Y. Kobayashi / Tetrahedron Letters 49 (2008) 7256–7259
7259
Note that the ortho lithiation is more convenient than the lithium–
bromine exchange of the corresponding bromide in that additional
steps are required for the preparation of bromide.
Claverie, C.; Roux, M.; Gennari, C. Angew. Chem., Int. Ed. 2003, 42, 234–236; (j)
Soorukram, D.; Knochel, P. Org. Lett. 2004, 6, 2409–2411; (k) Whitehead, A.;
McParland, J. P.; Hanson, P. R. Org. Lett. 2006, 8, 5025–5028; (l) Niida, A.;
Tanigaki, H.; Inokuchi, E.; Sasaki, Y.; Oishi, S.; Ohno, H.; Tamamura, H.; Wang,
Z.; Peiper, S. C.; Kitaura, K.; Otaka, A.; Fujii, N. J. Org. Chem. 2006, 71, 3942–
The present reaction is highlighted by reactions shown in en-
tries 6 and 7. Usually, Grignard preparation from alkenyl halides
suffers from isomerization of the double bond.1 In contrast, the
stereodefined alkenyllithiums generated from the corresponding
cis and trans 1-heptenyl iodides were transformed to copper com-
plexes, which furnished 2g and 2h without isomerization of the
olefin geometry.
3951; (m) Borthwick, S.; Dohle, W.; Hirst, P. R.; Booker-Milburn, K. I.
Tetrahedron Lett. 2006, 47, 7205–7208.
2
3
.
.
(a) Breit, B.; Demel, P. Adv. Synth. Catal. 2001, 343, 429–432; (b) Breit, B.;
Herber, C. Angew. Chem., Int. Ed. 2004, 43, 3790–3792; (c) Herber, C.; Breit, B.
Angew. Chem., Int. Ed. 2005, 44, 5267–5269; (d) Herber, C.; Breit, B. Chem. Eur. J.
2006, 12, 6684–6691; (e) Demel, P.; Keller, M.; Breit, B. Chem. Eur. J. 2006, 12,
6669–6683; (f) Rein, C.; Demel, P.; Outten, R. A.; Netscher, T.; Breit, B. Angew.
Chem., Int. Ed. 2007, 46, 8670–8673; (g) Herber, C.; Breit, B. Eur. J. Org. Chem.
007, 3512–3519.
2
In summary, we have established an organolithium-based ver-
sion of copper-assisted substitution of allylic picolinoates. The
preparations of organolithiums such as lithium–halogen exchange
and ortho lithiation were successfully coupled with the allylic sub-
stitution as delineated in Table 3, and thus providing another
advantage for the allylic substitution using allylic picolinoates.
4
(a) Breit, B.; Demel, P.; Studte, C. Angew. Chem., Int. Ed. 2004, 43, 3786–3789; (b)
Breit, B.; Demel, P.; Grauer, D.; Studte, C. Chem. Asian J. 2006, 1, 586–597.
5. (a) Harrington-Frost, N.; Leuser, H.; Calaza, M. I.; Kneisel, F. F.; Knochel, P. Org.
Lett. 2003, 5, 2111–2114; (b) Calaza, M. I.; Yang, X.; Soorukram, D.; Knochel, P.
Org. Lett. 2004, 6, 529–531; (c) Leuser, H.; Perrone, S.; Liron, F.; Kneisel, F. F.;
Knochel, P. Angew. Chem., Int. Ed. 2005, 44, 4627–4631; (d) Soorukram, D.;
Knochel, P. Angew. Chem., Int. Ed. 2006, 45, 3686–3689; (e) Soorukram, D.;
Knochel, P. Org. Lett. 2007, 9, 1021–1023; (f) Perrone, S.; Knochel, P. Org. Lett.
2
007, 9, 1041–1044.
Kiyotsuka, Y.; Acharya, H. P.; Katayama, Y.; Hyodo, T.; Kobayashi, Y. Org. Lett.
008, 10, 1719–1722.
7. Relative prices (Aldrich) of the major leaving groups as compared with picolinic
Acknowledgments
6.
2
This work was supported by a Grant-in-Aid for Scientific
Research from the Ministry of Education, Science, Sports, and
Culture, Japan. The authors thank Ms. M. Ishikawa of Center for
Advanced Materials Analysis, Technical Department, Tokyo
Institute of Technology, for HRMS analysis.
acid (28 $/mol):
Ph P@O)C CO
Purchased from Kanto Chemical, Japan.
9. Matsumura, K.; Hashiguchi, S.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1997, 119,
738–8739.
0. To an ice-cold suspension of CuBrꢀMe
were added PhLi (0.180 mL, 1.08 M in cyclohexane–Et
MgBr (1.40 mL, 0.20 M in THF, 0.280 mmol). After 30 min at 0 °C, a solution of
S)-1a (39.5 mg, 0.0960 mmol, 98% ee) in THF (1 mL) was added to it dropwise.
The resulting mixture was stirred at 0 °C for 1 h, and diluted with hexane and
saturated NH Cl with vigorous stirring. The layers were separated and the
aqueous layer was extracted with hexane twice. The combined extracts were
washed with brine, dried over MgSO , and concentrated to give a residue,
which was purified by chromatography on silica gel (hexane/EtOAc) to afford
C
6
F
5
2
CO H
43 times; o-(Ph
2
P)C
6
H
4
CO
2
H
330 times; o-
(
2
6
H
4
2
H available by oxidation of o-(Ph
2
P)C
6
H
4
CO
2
H.
8.
8
1
2
S (39.5 mg, 0.192 mmol) in THF (1.6 mL)
O, 0.194 mmol) and
2
References and notes
2
(
1
.
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4
4
2
.
1
(
R)-2a (34.0 mg, 97%). The H NMR spectrum of (R)-2a was identical with that
6
reported. Enantiomeric information (96% ee, 98% CT) was determined by HPLC
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R
0.5 mL/min, t /min = 51.2 (R), 54.4 (S).
1
1
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