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compositions of 3a at C3 and C4 were respectively assigned to
be 1.000 in this intramolecular KIE measurement. The 13C KIE
at C2 of 0.998(3)−0.999(4) indicated that the NMR measure-
ments were accurately performed, because a negligible 13C KIE
at C2 would be expected for either of the envisioned
mechanisms. We observed a substantial 13C KIE at C1 of
1.022(3)−1.025(4), which suggested that the reaction proceeds
via a stepwise mechanism. Additional mechanistic studies,
including DFT calculations, are currently ongoing in our
laboratory, since a concerted, though highly asynchronous
pathway couldn’t be completely excluded on the basis of the
current KIE study.
The reported general and highly enantioselective catalytic
[4+2]-cycloaddition of unactivated dienes with aldehydes was
enabled by the development of highly acidic and confined chiral
Brønsted acids. Our methodology provides an efficient and
enantioselective access to functionalized dihydropyrans and
potentially has an impact on the synthesis of fragrances, natural
products, and pharmaceuticals.
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
■
S
Additional detailed synthetic protocols and analytical data
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AUTHOR INFORMATION
Corresponding Author
ORCID
■
N.; Leutzsch, M.; Wang, Q.; Wakchaure, V.; List, B. Angew. Chem., Int.
Ed. 2014, 53, 8770. (c) James, T.; van Gemmeren, M.; List, B. Chem.
Rev. 2015, 115, 9388.
̌
̌
(17) (a) Coric, I.; List, B. Nature 2012, 483, 315. (b) Liao, S.; Coric, I.;
́
́
Wang, Q.; List, B. J. Am. Chem. Soc. 2012, 134, 10765. (c) Tsui, G. C.;
Liu, L.; List, B. Angew. Chem., Int. Ed. 2015, 54, 7703.
(18) (a) Nakashima, D.; Yamamoto, H. J. J. Am. Chem. Soc. 2006, 128,
9626. (b) Rueping, M.; Ieawsuwan, W.; Antonchick, A. P.; Nachtsheim,
B. J. Angew. Chem., Int. Ed. 2007, 46, 2097. (c) Sai, M.; Yamamoto, H. J.
J. Am. Chem. Soc. 2015, 137, 7091.
Notes
The authors declare no competing financial interest.
(19) (a) Kaib, P. S. J.; Schreyer, L.; Lee, S.; Properzi, R.; List, B. Angew.
Chem., Int. Ed. 2016, 55, 13200. (b) Lee, S.; Kaib, P. S. J.; List, B. J. J.
Am. Chem. Soc. 2017, 139, 2156.
(20) No desired cycloadducts were observed under our current
reaction conditons in the [4+2]-cycloadditions of benzaldehyde with
1,3-butadiene (CAS: 106-99-0), trans-1-phenyl-1,3-butadiene (CAS:
16939-57-4), 2,4-hexadiene (CAS: 592-46-1).
ACKNOWLEDGMENTS
■
Generous support from the Max Planck Society, the Alexander
von Humboldt Foundation (Fellowship to H.K. and Y.X.), the
Deutsche Forschungsgemeinschaft (Leibniz Award to B.L.), and
the European Research Council (Advanced Grant “C−H Acids
for Organic Synthesis, CHAOS”) are gratefully acknowledged.
We thank J. L. Kennemur and C. K. De for their suggestions
during the preparation of this paper and N. Tsuji for sharing
reagents. We are highly grateful to our analytical HPLC, GC,
NMR, MS, and X-ray departments for their excellent service. We
also thank D. A. Singleton (Texas A&M University), E. E. Kwan
(Harvard University) and M. Klußmann (Max-Planck-Institut
(21) Abate, A.; Allievi, M.; Brenna, E.; Fuganti, C.; Gatti, F. G.; Serra,
S. Helv. Chim. Acta 2006, 89, 177.
(22) Singleton, D. A.; Szymanski, M. J. J. Am. Chem. Soc. 1999, 121,
9455.
(23) Wolfsberg, M.; Van Hook, W. A.; Paneth, P.; Rebelo, L. P. N.
Isotope Effects in the Chemical, Geological, and Bio Sciences; Springer:
Dordrecht, 2010.
fur Kohlenforschung) for helpful discussions of 13C KIE
̈
(24) Singleton, D. A.; Merrigan, S. R.; Beno, B. R.; Houk, K. N.
Tetrahedron Lett. 1999, 40, 5817.
measurements. X-ray crystallographic data for the structures of
3f and 4c have been deposited in the Cambridge Crystallo-
graphic Data Centre database under accession code CCDC
1559570 and CCDC 1559571.
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