Journal of the American Chemical Society
Communication
cyclizations of polyenes are possible (Scheme 2b).30 For
instance, diene 49 is readily cyclized to cyclopentane 50, which
bears vicinal all-carbon quaternary centers, highlighting the
ability of carbon-centered radicals to overcome severe steric
clash via early transition states.31 This preliminary example
paves the way for a general approach to reductive mono- and
polycyclizations of unconjugated polyenes and a “traceless”
approach to fully saturated molecules like terpenes.32
The demonstrated utility of this new method for the
thermodynamic hydrogenation of alkenes illustrates its
potential to solve current and future problems in complex
molecule synthesis, especially the reduction of halogenated
alkenes (see Table 2b).33 Given the frequency with which
hydrogenations are employed and their breadth of applications
in chemistry, a new tool is advantageous. We expect that the
experimental ease, broad scope, and orthogonal stereo-
selectivity of HAT hydrogenation will lead to its extensive use.
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ASSOCIATED CONTENT
* Supporting Information
Experimental procedures and spectroscopic data. This material
■
S
́ ́
Angew. Chem., Int. Ed. 2007, 46, 4519. (f) Waser, J.; Gonzalez-Gomez,
J. C.; Nambu, H.; Huber, P.; Carreira, E. M. Org. Lett. 2005, 7, 4249.
(g) Waser, J.; Nambu, H.; Carreira, E. M. J. Am. Chem. Soc. 2005, 127,
8294. (h) Waser, J.; Carreira, E. M. Angew. Chem., Int. Ed. 2004, 43,
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AUTHOR INFORMATION
Corresponding Author
■
Present Address
†Department of Chemistry, Tohoku University, 6-3 Aoba-ku,
Sendai, 980-8578, Japan.
Author Contributions
‡These authors contributed equally.
(24) Taillier, C.; Bellosta, V.; Meyer, C.; Cossy, J. Org. Lett. 2004, 6,
2145.
Notes
(25) Fukuyma, T.; Tokuyama, H. Ald. Acta 2004, 37, 87.
(26) Weitkamp, A. W. J. Catal. 1966, 6, 431 Notably, many other
metal catalysts competitively isomerize 41 to Δ1,9-octalin, which is
hydrogenated to trans-decalin 42b. However, this thermodynamic
control is not general.
(27) Nishimura, S.; Mochizuki, F.; Kobayakawa, S. Bull. Chem. Soc.
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(28) Hatzellis, K.; Pagona, G.; Spyros, A.; Demetzos, C.;
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The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
Financial support for this work was provided by the NIH
(GM104180), the NSF GRFP (K.K.W.; DGE-1346837), and
the Italian Ministry for Education and Research (fellowship to
A.O.). We thank Professors Dale L. Boger, Phil S. Baran, and
Donna G. Blackmond for helpful conversations. We are grateful
to the Scripps Research Institute, Eli Lilly, Boehringer
Ingelheim, Amgen, and the Baxter Foundation for additional
financial support.
́
́
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Tetrahedron 2008, 64, 11822. (c) Leggans, E. K.; Barker, T. J.; Duncan,
K. K.; Boger, D. L. Org. Lett. 2012, 14, 1428.
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