R. Ma et al. / Tetrahedron 67 (2011) 1053e1061
1061
2. For special reviews, see: (a) Ye, L.-W.; Zhou, J.; Tang, Y. Chem. Soc. Rev. 2008, 37,
1140; (b) Cowen, B. J.; Miller, S. J. Chem. Soc. Rev. 2009, 38, 3102 For most recent
reports, see: (c) Fang, Y.-Q.; Jacobsen, E. N. J. Am. Chem. Soc. 2008, 130, 5660; (d)
Voituriez, A.; Panossian, A.; Fleury-Bregeot, N.; Retailleau, P.; Marinetti, A. J. Am.
Chem. Soc. 2008, 130, 14030; (e) Zhang, B.; He, Z.; Xu, S.; Wu, G.; He, Z. Tetra-
hedron 2008, 64, 9471; (f) Guo, H.; Xu, Q.; Kwon, O. J. Am. Chem. Soc. 2009, 131,
6318; (g) Xu, S.; Zhou, L.; Ma, R.; Song, H.; He, Z. Chem.dEur. J. 2009, 15, 8698;
(h) Meng, X.; Huang, Y.; Chen, R. Org. Lett. 2009, 11, 137; (i) Liang, Y.; Liu, S.; Yu,
Z.-X. Synlett 2009, 905; (j) Sampath, M.; Loh, T.-P. Chem. Commun. 2009, 1568;
(k) Zhang, Q.; Yang, L.; Tong, X. J. Am. Chem. Soc. 2010, 132, 2550.
3. (a) Quin, L. D. A Guide to Organophosphorus Chemistry; Wiley: New York, NY,
2000; (b) Valentine, D. H.; Hillhouse, J. H. Synthesis 2003, 317.
4. (a) Jung, C. K.; Wang, J. C.; Krische, M. J. J. Am. Chem. Soc. 2004, 126, 4118;
(b) Nair, V.; Biju, A. T.; Mohanan, K.; Suresh, E. Org. Lett. 2006, 8, 2213; (c) He, Z.;
Tang, X.; He, Z. Phosphorus, Sulfur Silicon Relat. Elem. 2008, 183, 1518; (d) Xu, S.;
Zhou, L.; Zeng, S.; Ma, R.; Wang, Z.; He, Z. Org. Lett. 2009, 11, 3498; (e) Xu, S.;
Zhou, L.; Ma, R.; Song, H.; He, Z. Org. Lett. 2010, 12, 544; (f) Khong, S. N.; Tran, Y.
S.; Kwon, O. Tetrahedron 2010, 66, 4760; (g) Xu, S.; Zou, W.; Wu, G.; Song, H.; He,
Z. Org. Lett. 2010, 12, 3556.
(CDCl3, 400 MHz, TMS):
d
7.28e6.86 (m, 5H), 6.24 (dd, J¼15.6,
1.6 Hz, 1H), 4.68 (dd, J¼10.0, 5.6 Hz, 1H), 4.58 (d, J¼3.2 Hz, 1H), 4.23
(q, J¼7.2 Hz, 2H), 1.98 (m, 1H), 1.78 (br s, 1H), 1.32 (t, J¼7.2 Hz, 3H),
1.15 (d, J¼6.6 Hz, 3H); 13C NMR (CDCl3, 100 MHz, TMS):
d 166.1,
153.3, 144.8, 130.1, 129.4, 123.9, 123.1, 120.9, 116.9, 74.7, 67.4, 60.6,
37.3, 14.2, 12.6 ppm. Anal. Calcd for C15H18O4: C, 68.68; H, 6.92;
found: C, 68.61; H, 6.72; HRMS (ESI) calcd for C15H18O4Naþ requires
285.1097, found 285.1101.
Following the general procedure, PPh3-mediated reactions of g-
ethyl allenoate 1d with 5-methoxy salicylaldehyde 4d (76 mg,
0.5 mmol) brought about the corresponding olefination product
3m (yellowish oil, 22 mg, yield 16%) and the annulation products
15b and 16b as an isomeric mixture (yellowish oil, 88 mg, yield 60%,
15b/16b ratio 1:1.2). For 3m, 1H NMR (CDCl3, 400 MHz, TMS):
d 6.85
(d, J¼8.8 Hz, 1H), 6.75 (dd, J¼8.8, 2.8 Hz, 1H), 6.64 (d, J¼2.8 Hz, 1H),
6.49 (s, 1H), 6.27 (d, J¼15.6 Hz, 1H), 5.82 (br s, 1H), 5.79 (dq, J¼15.6,
6.8 Hz, 1H), 4.19 (q, J¼7.2 Hz, 2H), 3.74 (s, 3H), 3.24 (s, 2H), 1.83 (dd,
J¼6.8, 1.0 Hz, 3H), 1.27 (t, J¼7.2 Hz, 3H); 13C NMR (CDCl3, 100 MHz,
5. For representative reactivity patterns of nonsubstituted allenoates with acti-
vated olefins or imines, see: (a) Zhang, C.; Lu, X. J. Org. Chem. 1995, 60, 2906; (b)
Xu, Z.; Lu, X. J. Org. Chem. 1998, 63, 5031.
6. (a) Zhu, X.-F.; Lan, J.; Kwon, O. J. Am. Chem. Soc. 2003, 125, 4716; (b) Wurtz, R. P.;
Fu, G. C. J. Am. Chem. Soc. 2005, 127, 12234; (c) Tran, Y. S.; Kwon, O. J. Am. Chem.
Soc. 2007, 129, 12632.
TMS):
d 172.6, 153.1, 147.6, 136.4, 133.3, 126.8, 126.5, 123.9, 117.1,
7. (a) Zhu, X.-F.; Henry, C. E.; Kwon, O. Tetrahedron 2005, 61, 6276; (b) Tang, X.;
Zhang, B.; He, Z.; Gao, R.; He, Z. Adv. Synth. Catal. 2007, 349, 2007; (c) Ung, A. T.;
Schafer, K.; Lindsay, K. B.; Pyne, S. G.; Amornraksa, K.; Wouters, R.; Van der
Linden, I.; Biesmans, I.; Lesage, A. S. J.; Skelton, B. W.; White, A. H. J. Org. Chem.
2002, 67, 227; (d) Cowen, B. J.; Miller, S. J. J. Am. Chem. Soc. 2007, 129, 10988.
8. (a) Zhu, X.-F.; Henry, C. E.; Wang, J.; Dudding, T.; Kwon, O. Org. Lett. 2005, 7,
1387; (b) Zhu, X.-F.; Schaffner, A.-P.; Li, R.-C.; Kwon, O. Org. Lett. 2005, 7, 2977;
(c) Creech, G. S.; Kwon, O. Org. Lett. 2008, 10, 429.
9. (a) Shi, Y.-L.; Shi, M. Org. Biomol. Chem. 2007, 5, 1499; (b) Hong, Y.; Shen, Z.; Mo,
W.; Hu, X. Chin. J. Org. Chem. 2009, 29, 1544; (c) Shi, Y.-L.; Shi, M. Chem.dEur. J.
2006, 12, 3374.
10. (a) Schweizer, E. E.; Meeder-Nycz, D. In The Chemistry of Heterocyclic Com-
pounds: Chromenes, Chromanes, Chromones; Ellis, G. P., Ed.; Wiley: New York,
NY, 1977; Vol. 31, pp 11e141; (b) Hepworth, J. In Comprehensive Heterocyclic
Chemistry; Katrizky, A. R., Rees, C. W., Eds.; Pergamon: Oxford, 1984; Vol. 3,
pp 737e883.
114.8, 114.3, 61.4, 55.7, 34.5, 18.4, 14.1 ppm; HRMS (ESI) calcd for
C16H20O4Naþ requires 299.1254, found 299.1254. Selected data for
15b, 1H NMR (CDCl3, 400 MHz, TMS):
d 7.00, 6.78 (m, 4H), 6.15 (dd,
J¼15.6, 1.6 Hz, 1H), 4.35 (m, 2H), 4.20 (q, J¼7.2 Hz, 2H), 3.74 (s, 3H),
2.41 (br s, 1H), 1.83 (m, 1H), 1.30 (t, J¼7.2 Hz, 3H), 1.16 (d, J¼6.8 Hz,
3H); 13C NMR (CDCl3, 100 MHz, TMS):
d 166.1, 153.9, 147.0, 144.7,
125.3, 122.6, 117.1, 115.6, 111.7, 78.2, 70.8, 60.6, 55.6, 40.2, 14.2,
12.4 ppm. Selected data for 16b, 1H NMR (CDCl3, 400 MHz, TMS):
d
7.00, 6.78 (m, 4H), 6.19 (dd, J¼15.6, 1.6 Hz, 1H), 4.58 (dd, J¼10.0,
5.6 Hz,1H), 4.49 (d, J¼3.2 Hz,1H), 4.21 (q, J¼7.2 Hz, 2H), 3.74 (s, 3H),
2.41 (br s, 1H), 1.95 (m, 1H), 1.31 (t, J¼7.2 Hz, 3H), 1.15 (d, J¼6.8 Hz,
3H); 13C NMR (CDCl3, 100 MHz, TMS):
d 166.1, 153.5, 147.1, 145.1,
124.1, 122.8, 117.5, 116.4, 113.5, 74.7, 67.4, 60.5, 55.6, 37.3, 14.1,
12.4 ppm. Anal. Calcd for C16H20O5: C, 65.74; H, 6.90; found: C,
65.57; H, 7.12; HRMS (ESI) calcd for C16H20O5Naþ requires 315.1203,
found 315.1208.
11. (a) Shi, Y.-L.; Shi, M. Org. Lett. 2005, 7, 3057; (b) Zhao, G.-L.; Shi, Y.-L.; Shi, M. Org.
Lett. 2005, 7, 4527; (c) Dai, L.-Z.; Shi, Y.-L.; Zhao, G.-L.; Shi, M. Chem.dEur. J.
2007, 13, 3701; (d) Kumar, N. N. B.; Reddy, M. N.; Swamy, K. C. K. J. Org. Chem.
2009, 74, 5395; (e) Ref. 2h; (f) Meng, X.; Huang, Y.; Zhao, H.; Xie, P.; Ma, J.; Chen,
R. Org. Lett. 2009, 11, 991.
12. Tang, X. Some New CarboneCarbon Bond Forming Reactions Catalyzed by P, N
Organocatalysts. Master Degree Dissertation, Nankai University, 2007.
13. For typical examples, see: (a) Creech, G. S.; Zhu, X.-F.; Fonovic, B.; Dudding, T.;
Kwon, O. Tetrahedron 2008, 64, 6935 and references cited therein; (b) Ref. 2i.
14. Selected crystal data for trans-5j (CCDC 790991): empirical formula:
C14H14ClO4. Formula weight: 281.70. Crystal space group: orthorhombic, Pccn.
Acknowledgements
Financial support from National Natural Science Foundation of
China (Grant no. 20872063) is gratefully acknowledged.
¼90ꢀ,
ꢀ
ꢀ
ꢀ
a
Unit cell dimensions: a¼12.847 (3) A, b¼28.563 (6) A, c¼7.4684 (15) A,
3
ꢀ
b
¼90ꢀ,
g
¼90ꢀ. F000¼1176, Z¼8, Dcalcd¼1.366 g cmꢁ3, U¼2740.5 (10) A , T¼294
ꢀ
(2) K,
l
(Mo K
a
)¼0.7107 A. 2378 reflections collected in the range of 1.43ꢃ
qꢃ25.
02ꢀ, Rint¼0.0753. Refinement method: full-matrix least-squares on F2 to R1¼0.
0865, wR2¼0.2040. The supplementary crystallographic data for this com-
pound can be obtained free of charge from The Cambridge Crystallographic
Supplementary data
General experiment conditions; spectroscopic and analytical
data for compounds 3 and 5; more details in structure de-
termination of chromans 5 by 1H NMR data; ORTEP drawing of
trans-5j; NOESY spectra for cis-5i and trans-5k; 1H and 13C NMR
spectroscopic copies for all new compounds in this study. Supple-
mentary data associated with this article can be found in online
files and InChIKeys of the most important compounds described in
this article.
15. In the phosphine-catalyzed [3þ2] cycloaddition of allenoates with activated
olefins, a stepwise mechanism and the involvement of water in the proton
transfer have been confirmed experimentally and theoretically: (a) Xia, Y.;
Liang, Y.; Chen, Y.; Wang, M.; Jiao, L.; Huang, F.; Liu, S.; Li, Y.; Yu, Z.-X. J. Am.
Chem. Soc. 2007, 129, 3470; (b) Mercier, E.; Fonovic, B.; Henry, C.; Kwon, O.;
Dudding, T. Tetrahedron Lett. 2007, 48, 3617; (c) Liang, Y.; Liu, S.; Xia, Y.; Li, Y.;
Yu, Z.-X. Chem.dEur. J. 2008, 14, 4361; (d) Ref. 2i.
16. Although the deuterium-labeling experiments [Eqs. 2 and 3] provide sup-
portive evidence on the plausible mechanism of the [4þ2] annulation, it is
noteworthy that no detectable deuterium incorporation at the g-carbon of the
allenoate 1a-d3 or 1a was observed in the product 5i-d4. Our speculation is that
the resonance form 6b should be a minor contributor to the formation of the
intermediate 8 (Scheme 2).
References and notes
17. The phosphorus ylide derived from trialkylphosphine is more reactive in the
Wittig reaction. Also see: Maryanoff, B. E.; Reitz, A. B. Chem. Rev. 1989, 89, 863.
1. For leading reviews, see: (a) Lu, X.; Zhang, C.; Xu, Z. Acc. Chem. Res. 2001, 34,
535; (b) Methot, J. L.; Roush, W. R. Adv. Synth. Catal. 2004, 346, 1035; (c) Ma,
S. Chem. Rev. 2005, 105, 2829; (d) Ma, S. Aldrichimica Acta 2007, 40, 91;
(e) Marinetti, A.; Voituriez, A. Synlett 2010, 174; (f) Xu, S.; He, Z. Sci. Sin.
Chim. 2010, 40, 856.
18. A [3þ2] annulation product from
g-ethyl allenoate 1d and p-trifluoromethyl
benzaldehyde was isolated in 19% yield after the reaction was run under the
mediation of P(4-FC6H4)3 (10 mol %) in xylene at rt for a week. See Ref. 2g.
19. Daigle, D. J. Inorg. Synth. 1998, 32, 40.