S.-Y. Zhang et al. / Tetrahedron Letters 50 (2009) 4178–4181
4181
H–[Rh]–H followed by b-H elimination in I-a,7 since aldehyde is
much less reactive toward the radical addition of I-a than olefin.
Then aldol condensation gave the product of Type A (R1 = H), or
double aldol processes of I-b accomplished Type B reaction
(R1 = alkyl). In path B, the [Rh] oxidation of the alcohols gave the
corresponding aldehyde II-b and metal dihydride intermeditate,8
5. For recent selected examples of transition metal-catalyzed C–C cross-coupling
between ketones and alcohols under base conditions, see: (a) Cho, C. S.; Kim, B.
T.; Lee, M. J.; Kim, T.-J.; Shim, S. C. Angew. Chem., Int. Ed. 2001, 40, 958–960; (b)
Cho, C. S.; Kim, B. T.; Kim, T.-J.; Shim, S. C. J. Org. Chem. 2001, 66, 9020–9022; (c)
Nishibayashi, Y.; Wakiji, I.; Ishii, Y.; Uemura, S.; Hidai, M. J. Am. Chem. Soc. 2001,
123, 3393–3394; (d) Edwards, M. G.; Williams, J. M. J. Angew. Chem., Int. Ed.
2002, 41, 4740–4743; (e) Taguchi, K.; Nakagawa, H.; Hirabayashi, T.; Sakaguchi,
S.; Ishii, Y. J. Am. Chem. Soc. 2004, 126, 72–73; (f) Edwards, M. G.; Jazzar, R. F. R.;
Panie, B. M.; Shermer, D. J.; Whittlesey, M. K.; Williams, J. M. J.; Edney, D. D.
Chem. Commun. 2004, 90–91; (g) Kwon, M. S.; Kim, N.; Seo, S. H.; Park, I. S.;
Cheedrala, R. K.; Park, J. Angew. Chem., Int. Ed. 2005, 44, 6913–6915; (h) Onodera,
G.; Nishibayashi, Y.; Uemura, S. Angew. Chem., Int. Ed. 2006, 45, 3819–3822; (i)
Yamada, Y. M. A.; Uozumi, Y. Org. Lett. 2006, 8, 1375–1378; (j) Black, P. J.;
Edwards, M. G.; Williams, J. M. J. Eur. J. Org. Chem. 2006, 4367–4378; (k) Yamada,
Y. M. A.; Uozumi, Y. Tetrahedron 2007, 63, 8492–8498; (l) Mierde, H. V.; Voort, P.
V. D.; Vos, D. D.; Verpoort, F. Eur. J. Org. Chem. 2008, 9, 1625–1631.
and followed by an aldol condensation to give the a,b-unsaturated
aldehydes, or a double aldol condensation to yield the diarylidene
ketone compounds. No reduction products could be received in our
experimental. Further synthetic application of these reactions is
currently continued in our group.
6. A LiClO4-amine mediated direct aldol process between ketones and alcohols by
contemporary aldol-Tishchenko methodologies, see: Markert, M.; Mahrwald, R.
Synthesis 2004, 1429–1433.
Acknowledgments
7. Branchaud, B. P.; Choi, Y. L. Tetrahedron Lett. 1988, 29, 6037–6038.
8. Santosh Laxmi, Y. R.; Bäckvall, J.-E. Chem. Commun. 2000, 611–612.
We thank the financial support of NSFC (Nos. 20621091,
20672048 and 20732002) and the ‘111’ Program of Chinese Educa-
tion Ministry.
9. General procedure: To
a flame-dried 25 mL flask were sequentially added
toluene (4 mL), alcohol (2.5 mmol), and RhCl(PPh3)3 (20 mg, 0.02 mmol) under
argon atmosphere. The reaction system was stirred at 30 °C for 20 min. The
aldehyde (1 mmol) was added and stirred at 30 °C for 20 min, and then the
freshly distilled BF3ÁOEt2 (0.15 mL, 1.2 mmol) was added. The reaction was
heated using oil bath to 80 °C, and stirred at 80 °C for further 8–18 h until
TLC analysis showed the reaction was completed. Then the reaction was
cooled to rt, and diluted with ethyl acetate (3 mL) followed by addition of
saturated aqueous NaHCO3 (3 mL). The organic layer was separated, and the
aqueous phase was re-extracted with ethyl acetate (3Â3 mL). The combined
organic extracts were washed with brine (10 mL), dried over dried Na2SO4,
and purified by the flash chromatography to afford the desired
products.Spectral data for selected products: Compound 3c: 1H NMR (CDCl3,
400 MHz, ppm): d 1.77–1.80 (m, 2H), 2.91–2.95 (m, 4H), 7.32–7.48 (m, 10H),
7.82 (s, 2H); 13C NMR (CDCl3, 100 MHz, ppm) 22.9, 28.4, 128.3, 128.5, 130.3,
135.9, 135.1, 136.9, 190.3; MS m/z (%) 274 (M+, 68), 273 (100), 247 (5), 217
(24), 169 (10), 141 (11), 128 (16), 115 (31).Compound 3l: 1H NMR (CDCl3,
400 MHz, ppm): d 1.94 (d, J = 0.8 Hz, 3H), 7.25 (m, 1H), 7.37–7.45 (m, 3H),
7.66 (d, J = 8.0 Hz, 1H), 9.68 (s, 1H); 13C NMR (CDCl3, 100 MHz, ppm) 10.8,
References and notes
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(
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(