Scheme 8. Formation of predominant 1,2-addition cycloadduct 19
Supplementary Material
Supplementary material to this article can be found online at
Conclusions
An intramolecular oxidopyrylium-alkene [5+2] cycloaddition of
a silicon-tethered BOC-pyranone was successfully implemented
toward formation of a tricyclic core of toxicodenane A. The
precursor to the [5+2] cycloaddition was constructed via Feist-
Benary furan annulation, Achmatowicz oxidative rearrangement,
and BOC-protection of the lactol. Conjugate addition to the
cycloadduct enone was unsuccessful, but cleanly delivered the
1
,2-addition adduct. Future studies will include efforts toward
alternative tethers, including allenes, en route to toxicodenane A.
Acknowledgments
Acknowledgment is made to the National Science Foundation
(
(
NSF) for individual research award (CHE-1565644) and NMR
CHE-0722385), SC-XRD (CHE-1039689), and MS (CHE-
1
337497) analyses from departmental instrumentation obtained
from the Major Research Instrumentation (MRI) program. JPG
acknowledges the ACS-DOC Summer Undergraduate Research
Fellowship (SURF) sponsored by Biogen/Pfizer. We thank Dr.
John Goodell for helpful discussions and Mr. Riley Kaufman for
assistance with the synthesis of starting materials.
Synthetic efforts toward the tricyclic core of (±)-
toxicodenane A are reported
Crystallographic Data
Crystallographic data (excluding structure factors) for the
structures in this paper have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication
number 2009209 CCDC. Copies of the data can be obtained, free
of charge, on application to CCDC.
Feist-Benary, Achmatowicz, Boc-protection used to
construct precursor
Oxidopyrylium-based [5+2] cycloaddition of Boc-
pyranone-vinyl silane
References
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(6) Kobayashi, T.; Yamanoue, K.; Abe, H.; Ito, H. Eur. J. Org. Chem.
2
.
2
017, 6693-6699.
(
1) He, J.-B.; Luo, J.; Zhang, L.; Yan, Y.-M.; Cheng, Y.-X. Org. Lett. 2013,
5, 3602-3605.
(7) (a) Bulandr, J. J.; Grabowski, J. P.; Law, C. M; Shaw, J. L.; Goodell, J.
R. Mitchell, T. A. J. Org. Chem. 2019, 84, 10306-10320. (b) Kaufman,
R. H.; Law, C. H.; Simanis, J. A..; Woodall, E. L.; Zwick III, C. R.;
Wedler, H. B.; Wendelboe, P.; Hamaker, C. G.; Goodell, J. R.; Tantillo,
D. J.; Mitchell, T. A. J. Org. Chem. 2018, 83, 9318-9338. (c) Simanis,
J. A.; Zwick III, C. R.; Woodall, E. L.; Goodell, J. R.; Mitchell, T. A.
Heterocycles, 2015, 91, 149-156. (d) Simanis, J. A.; Law, C. M.;
Woodall, E. L.; Hamaker, C. G.; Goodell, J. R.; Mitchell, T. A. Chem.
Commun. 2014, 50, 9130-9133. (e) Woodall, E. L.; Simanis, J. A.;
Hamaker, C. G.; Goodell, J. R.; Mitchell, T. A. Org. Lett. 2013, 15,
32L70e-a32v7e3. this area blank for abstract info.
1
(2) Qin, G.-F.; Liang, H.-B.; Liu, W.-X.; Zhu, F.; Li, P.-L.; Li, G.-Q.; Yao,
J.-C. Molecules 2019, 24, 3912.
(3) He, J.-B.; Lu, Q.; Cheng, Y.-X. Helv. Chim. Acta 2015, 98, 1004-1008.
(
4) (a) Min, L.; Liu, X.; Li, C.-C. Acc. Chem. Res. 2020, 53, 703-718. (b)
Gao, K.; Zhang, Y.-G.; Wang, Z.; Ding, H. Chem. Commun. 2019, 55,
Eff o1 8r 5t 9s - t1 o8 7w 8 a. r( cd) Xt h. eL i tu o, tYa . -l J s. yH nu t, hJ . e- Hs i. sF oa nf ,( J±. )Z - ht ao o x, iSc .o Ldi ea nn da nC e. -C. Li,
Org. Chem. Front. 2018, 5, 1217-1228. (d) Ylijoki, K. E. O.; Stryker, J.
A utilizing an oxidopyrylium-based [5+2]
M. Chem. Rev. 2013, 113, 2244-2266. (e) Nguyen, T. V.; Hartmann, J.
(8) (a) Seki, M.; Sakamoto, T.; Suemune, H. Kanematsu, K. J. Chem. Soc.,
Perkin Trans. 1 1997, 1707-1714. (b) Ogino, T.; Jurihara, C.; Baba, Y.;
cycloaddition of a silicon-tethered BOC-pyranone
M.; Enders, D. Synthesis 2013, 45, 845-873. (f) Battiste, M. A.;
Jacob P. Grabowski, Gregory M. Ferrence, and T. Andrew Mitchell
Pelphrey, P. M. Wright, D. L. Chem. Eur. J. 2006, 12, 3438-3447.
Kanematsu, K. J. Chem. Soc., Chem. Commun. 1994, 1979-1980.
(
5) (a) Bejcek, L. P.; Murelli, R. P. Tetrahedron 2018, 74, 2501-2521. (b)
(9) (a) Ji, Y.; Benkovics, T.; Beutner, G. L.; Sfouggatakis, C.; Eastgate, M.
D.; Blackmond, D. G. J. Org. Chem. 2015, 80, 1696-1702. (b)
Georgiadis, M. P.; Albizati, K. F.; Georgiadis, T. M. Org. Prep. Proc.
Int. 1992, 24, 95-118. (c) Achmatowicz, O.; Szechner, P. B. B.;
Zwierzchowska, Z.; Zamojski, A. Tetrahedron 1971, 27, 1973-1996. (d)
Singh, V.; Krishna, U. M.; Vikrant, Trivedi, G. K. Tetrahedron, 2008,
6
6
4, 3405-3428. (c) Mascareñas, J. L. Advances in Cycloaddition, 1999,
, 1-54.