K.A. Parker, T.L. Mindt / Tetrahedron 67 (2011) 9779e9786
9785
and vinyl stannane 2 (mixture of cis/trans isomers) according to
the general procedure 2; reaction time: 7 h. Pale yellow oil
(320 mg, 69%, mixture of 7:1 trans/cis isomers): IR (neat) 2955,
2877, 1745, 1469, 1415, 1223, 1092, 925, 741 cmꢂ1 1H NMR
(CD2Cl2) 6.75 and 6.52 (each s, total 1H, trans/cis 7:1 in the
Supplementary data
n
Supplementary data associated with this article can be found, in
;
d
order given), 6.71 and 6.65 (each br d, total 1H, 3J¼15.9 and
11.8 Hz, respectively, trans/cis 7:1 in the order given), 6.05 and
5.81 (each dt, total 1H, 3J¼15.9, 7.1 and 3J¼11.8, 7.4 Hz, re-
spectively, trans/cis 7:1 in the order given), 3.70 and 3.69 (each s,
total 3H, trans/cis 7:1 in the order given), 3.28 and 3.24 (each dd,
total 2H, 3J¼7.4 Hz, 4J¼1.8 Hz and 3J¼7.1 Hz, 4J¼1.3 Hz, re-
spectively, cis/trans 1:7 in the order given), 2.14, 2.13 and 2.12
(each s, total 6H, trans/cis isomers), 1.07e0.88 (m, 18H),
References and notes
1. See Parker, K. A.; Mindt, T. L.; Koh, Y.-H. Org. Lett. 2006, 8, 1759e1762 and
references therein.
2. Stannane 2 was used as a mixture of cis/trans isomers: Collins, P. W.; Kramer, S.
W.; Gasiecki, A. F.; Weier, R. M.; Jones, P. H.; Gullikson, G. W.; Bianchi, R. G. J.
Med. Chem. 1987, 30, 193e197.
3. Parker, K. A.; Mindt, T. L. Org. Lett. 2001, 3, 3875e3878.
4. For selected recent references to the synthesis of chromene structures see: (a)
Bera, K.; Sarkar, S.; Biswas, S.; Maiti, S.; Jana, U. J. Org. Chem. 2011, 76,
3539e3544; (b) Ye, L.-W.; Sun, X.-L.; Zhu, C.-Y.; Tang, Y. Org. Lett. 2006, 8,
3853e3856; (c) Lu, G.; Malinakova, H. C. J. Org. Chem. 2004, 69, 4701e4715; (d)
Kurdyumov, A. V.; Hsung, R. P.; Ihlen, K.; Wang, J. Org. Lett. 2003, 5, 3935e3938;
(e) Yavari, I.; Bayat, M. Tetrahedron 2003, 59, 2001e2005.
0.84e0.65 (m, 12H) ppm; 13C NMR (CD2Cl2)
d 172.6, 172.5, 148.6,
148.0, 147.0, 146.5, 140.5, 133.7, 130.4, 129.3, 128.8, 128.5, 126.4,
125.5, 123.3, 121.3, 117.1, 113.4, 52.2, 52.1, 39.0, 34.6, 14.4, 14.3,
14.1, 13.6, 7.09, 7.08 6.2, 6.0, 5.84, 5.78, ppm; LRFAB-MS:
[M]þ¼464 (calcd for C25H44O4Si2: 464).
5. See also Ref. 3 and citations therein.
6. Chromene natural products that have stimulated recent interest include the
tuberatolides (FXR antagonists), the thiaplidiaquinones (pro-apoptotic), and
members of the puupehenone series (many activities). See: (a) Choi, H.; Hwang,
H.; Chin, J.; Kim, E.; Lee, J.; Nam, S.-J.; Lee, B. C.; Rho, B. J.; Kang, H. J. Nat. Prod.
2011, 74, 90e94; (b) Aiello, A.; Fattorusso, E.; Luciano, P.; Macho, A.; Menna, M.;
Munoz, E. J. Med. Chem. 2005, 48, 3410e3416 and; Aiello, A.; Fattorusso, E.;
Luciano, P.; Menna, M.; Calzado, M. A.; Munoz, E.; Bonadies, F.; Guiso, M.;
Sanasi, M. F.; Cocco, G.; Nicoletti, R. Bioorg. Med. Chem. 2010, 18, 719e727; (c)
For a leading reference, see Utkina, N. K.; Denisenko, V. A.; Krasokhin, V. B.
Tetrahedron Lett. 2011, 52, 3765e3768.
7. For a recent example of preparative chemistry based on the sunlight-activated
photochemistry of quinones, see, (a) Schiel, C.; Oelgemoeller, M.; Ortner, J.;
Mattay, J. Green. Chem. 2001, 3, 224e228 For reviews, see; (b) Finley, K. T.;
Quinones in Kirk-othmer Encyclopedia of Chemical Technology, 5th ed.; 2006; Vol.
21 236e270 and Maruyama, K.; Osuka, A. Recent Advances in the Photo-
chemistry of Quinones In. Chem. Quinonoid Compd.; Patai, S., Rappoport, Z., Eds.;
1988; Vol. 2, pp 759e878 Pt. 1.
4.3.16. TES-protected vinyl hydroquinone 10d. From TES-protected
bromohydroquinone 9d (448 mg, 1.00 mmol) and vinyl stannane
2 (mixture of cis/trans isomers) according to the general procedure
2; reaction time: 20 h. Pale yellow oil (195 mg, 42%; mixture of
trans/cis isomers 5:1): IR (neat)
n
2956, 2878, 1743, 1477, 1227, 1192,
6.79 and 6.67 (each
1160, 1007, 908, 732 cmꢂ1; 1H NMR (CD2Cl2)
d
dt, total 1H, 3J¼16.2 Hz, 4J¼1.4 Hz and 3J¼11.5 Hz, 4J¼1.5 Hz, re-
spectively, trans/cis 5:1 in the order given), 6.56 and 6.40 (each d,
total 1H, 4J¼2.7 Hz and 4J¼2.8 Hz, respectively, trans/cis 5:1 in the
order given), 6.35 and 6.33 (each d, total 1H, 4J¼2.7 Hz and
4J¼2.8 Hz, respectively, trans/cis 5:1 in the order given), 6.17 and
5.85 (each dt, total 1H, 3J¼16.2, 7.1 Hz and 3J¼11.5, 7.4 Hz, trans/cis
5:1 in the order given), 3.77 and 3.76 (each s, total 3H, cis/trans 1:5
in the order given), 3.71 and 3.69 (each s, total 3H, trans/cis 5:1 in
the order given), 3.28 and 3.26 (each dd, total 2H, 3J¼7.4 Hz,
4J¼1.5 Hz and 3J¼7.1 Hz, 4J¼1.4 Hz, respectively, cis/trans 1:5 in the
order given),1.09e0.91 (m,18H), 0.83e0.65 (m,12H) ppm; 13C NMR
8. Iwamoto, H.; Takuwa, A.; Hamada, K.; Fujiwara, R. J. Chem. Soc., Perkin Trans. 1
1999, 575e581.
9. Parker, K. A.; Mindt, T. L. Org. Lett. 2002, 4, 4265e4268.
10. We also found that addition of base (Et3N, DIPEA, K2CO3) and oxidizing agents
(DDQ, O2), intended to accelerate the enolization step or to recycle hydroqui-
none side products in-situ, led to rapid degradation of substrates and/or in-
termediates in each case even at low temperature.
11. We note the resemblance of this phosphine oxide promoted isomerization to
the acid-catalyzed oxa-6pi electrocyclization observed by Jurd and studied in
detail by Bishop, et al. See (a) Jurd, L. Tetrahedron 1977, 33, 163e168; (b) Bishop,
L. M.; Winkler, M.; Houk, K. N.; Bergman, R. G.; Trauner, D. Chem.dEur. J. 2008,
14, 5405e5408.
12. A related enolization/electrocyclization has been suggested as the mechanism
of the thermal isomerization of 2-demethylplastoquinone-3 to 7-
demethylplastichromenol-2, see: Muckensturm, B.; Diyani, F.; Reduron, J.-P.;
Hildenbrand, M. Phytochemistry 1997, 45, 549e550.
13. For a relevant review see: Ferreira, S. B.; da Silva, F. de C.; Pinto, A. C.; Gonzaga,
D. T. G.; Ferreira, V. F. J. Heterocycl. Chem. 2009, 46, 1080e1097.
14. For recent reviews on multicatalysis, see: (a) Ambrosini, L. M.; Lambert, T. H.
ChemCatChem 2010, 2, 1373e1380; (b) Ramachary, D. B.; Jain, S. Org. Biomol.
Chem. 2011, 9, 1277e1300; (c) Walji, A. M.; MacMillan, D. W. C. Synlett 2007,
1477e1489; (d) Chapman, C. J.; Frost, C. G. Synthesis 2007, 1e21; (e) Wasilke, J.-
C.; Obrey, S. J.; Baker, R. T.; Bazan, G. C. Chem. Rev. 2005, 105, 1001e1020.
15. The circular arrow notation in Scheme 4 is a convention introduced by Lam-
bert; see: Cernak, T. A.; Lambert, T. H. J. Am. Chem. Soc. 2009, 131, 3124e3125
and Ref. 14a. It is similar to notations for multicatalysis used in Refs. 14cee.
16. Ellis, G. P. Chemistry of Heterocyclic Compounds ‘Chromenes, Chromanones and
Chromones’; John: New York, NY, 1977; Vol. 31; 11e141.
(CD2Cl2)
d 172.6, 172.4, 151.8, 150.2, 149.8, 148.9, 138.2, 137.9, 129.3,
129.2, 129.1, 128.9, 124.0, 122.6, 112.3, 108.4, 104.5, 104.4, 56.5, 55.7,
52.2, 52.0, 39.0, 34.7, 7.2, 7.1, 6.1, 5.6 ppm; LRFAB-MS:
[MþNa]þ¼489 (calcd for C24H42O5Si2Na: 489).
4.3.17. 1,3,4-Trimethoxyphenyl butenoate 12. From 2-bromo-1,3,4-
trimethoxybenzene (11)32 (151 mg, 0.61 mmol) and vinyl stannane
2 (mixture of cis/trans isomers) according to general procedure 2;
reaction time: 18 h. Pale yellow oil (84 mg, 52%, mixture of trans/cis
isomers 3:1): IR (neat)
n
2951, 2837, 1738, 1483, 1257, 1164, 1100,
6.82 and 6.78 (each d, total 1H,
796 cmꢂ1 1H NMR (CD2Cl2)
;
d
3J¼9.0 Hz, cis/trans 1:3 in the order given), 6.79e6.64 (m, 1.75H),
6.59 (d, 0.75H, 3J¼9.0 Hz, trans-isomer), 6.40 (dt, 0.25H, 3J¼11.3 Hz,
4J¼1.6 Hz, cis-isomer), 5.97 (dt, 0.25H, 3J¼11.3, 7.2 Hz, cis-isomer),
3.80, 3.79, 3.78, 3.76, 3.72, 3.69, 3.66 and 3.65 (each s, total 12H),
3.26 (d, 1.5H, 3J¼6.2 Hz, trans-isomer), 3.01 (dd, 0.5H, 3J¼7.2 Hz,
17. Takanashi, S.-I.; Mori, K. Liebigs Ann./Recl. 1997, 825e838.
4J¼1.6 Hz, cis-isomer) ppm; 13C NMR (CD2Cl2)
d 172.8, 172.7, 152.8,
18. Guzikowski, A. P.; Cai, S. X.; Espitia, S. A.; Hawkinson, J. E.; Huettner, J. E.;
Nogales, D. F.; Tran, M.; Woodward, R. M.; Weber, E.; Keana, J. F. W. J. Med.
Chem. 1996, 39, 4643e4653.
151.9,148.6,148.1,147.8,147.7,120.6, 127.5,126.6, 124.6, 123.5, 120.4,
112.3,111.9,106.4,106.1. 40.3, 35.5, 60.6, 56.72, 56.70, 56.4, 56.2, 52.2,
52.0 ppm; LRFAB-MS: [MþNa]þ¼289 (calcd for C14H18O5Na: 289).
19. Zhu, J.; Beugelmans, R.; Bigot, A.; Singh, G. P.; Bois-Choussy, M. Tetrahedron Lett.
1993, 34, 7401e7404.
20. For a similar system, Bishop et al. (Ref. 11b) calculated a
the oxa-6 rearrangement in the gas phase
D
Gz of 19.8 kcal/mol for
p
Acknowledgements
21. McKean, D. R.; Parrinello, G.; Renaldo, A. F.;Stille, J. K. J. Org. Chem.1987, 52, 422e424.
22. Similar reduced products have been seen in (Ph3P)4Pd catalyzed couplings by
others; see, for example, Chan, K. S.; Mak, C. C. Tetrahedron 1994, 50,
2003e2016.
23. Bumagin, N. A.; Bumagina, I. G.; Beletskaya, I. P. Dokl. Akad. Nauk SSSR 1984,
274, 818e822.
24. Williams, D. R.; Myers, B. J.; Mi, L. Org. Lett. 2000, 2, 945e948.
25. Blatchly, J. M.; Green, R. J. S.; McOmie, J. F. W.; Searle, J. B. J. Chem. Soc. C 1969,
1353e1358.
26. (a) Norris, R. K.; Sternhell, S. Aust. J. Chem. 1966, 19, 617; (b) Cameron, D. W.;
Crossley, M. J. Aust. J. Chem. 1978, 31, 617e627.
This work was supported by the National Institutes of Health
(CA-87503 and GM 74776) and a fellowship of the Graduate As-
sistance in Areas of National Need program of the U.S. Department
of Education. We thank Dr. Tun Li Shen (Brown University) for mass
spectroscopic measurements and Dr. Fernando Raineri and Dr.
Jonathan G. Rudick (Stony Brook University) for valuable
discussions.