ORGANIC
LETTERS
XXXX
Vol. XX, No. XX
000–000
Regioselective Ruthenium Catalyzed
Hydrohydroxyalkylation of Dienes with
3‑Hydroxy-2-oxindoles: Prenylation,
Geranylation, and Beyond
Te-Yu Chen and Michael J. Krische*
University of Texas at Austin, Department of Chemistry and Biochemistry, Austin,
Texas 78712, United States
Received April 26, 2013
ABSTRACT
The direct conversion of secondary to tertiary alcohols via ruthenium(0) catalyzed CÀC coupling of substituted 3-hydroxy-2-oxindoles with
various dienes is described. Coupling occurs in a completely regioselective manner in the absence of stoichiometric byproducts.
In the course of exploring hydrogen-mediated CÀC coupl-
ings outside of hydroformylation,1 our laboratory has
developed metal catalysts that promote the transfer of
hydrogen from primary alcohols to various π-unsaturated
compounds resulting in generation of aldehydeÀ
organometallic nucleophileÀelectrophile pairs that com-
bine to form products of aldehyde addition. These pro-
cesses merge redox and CÀC bond construction events,2
bypassing both discrete alcohol-to-aldehyde oxidation and
the stoichiometric use of premetalated reagents. Although
conditions for the CÀC coupling of primary alcohols
to dienes3À5 and other π-unsaturated reactants (allenes,
enynes, alkynes and allylic acetates)1 have been developed,
corresponding couplings of secondary alcohols have pro-
ven more challenging.
(5) For ruthenium catalyzed transfer hydrogenative reductive cou-
pling of dienes to paraformaldehyde, see: Smejkal, T.; Han, H.; Breit, B.;
Krische, M. J. J. Am. Chem. Soc. 2009, 131, 10366.
(6) A related oxidative coupling pathway is observed in ruthenium(0)
catalyzed PausonÀKhand type reactions of 1,2-diones: (a) Chatani, N.;
Tobisu, M.; Asaumi, T.; Fukumoto, Y.; Murai, S. J. Am. Chem. Soc.
1999, 121, 7160. (b) Tobisu, M.; Chatani, N.; Asaumi, T.; Amako, K.; Ie,
Y.; Fukumoto, Y.; Murai, S. J. Am. Chem. Soc. 2000, 122, 12663.
(7) For nickel catalyzed intermolecular diene-aldehyde reductive
coupling, see: (a) Kimura, M.; Ezoe, A.; Shibata, K.; Tamaru, Y.
J. Am. Chem. Soc. 1998, 120, 4033. (b) Takimoto, M.; Hiraga, Y.; Sato,
Y.; Mori, M. Tetrahedron Lett. 1998, 39, 4543. (c) Kimura, M.;
Fujimatsu, H.; Ezoe, A.; Shibata, K.; Shimizu, M.; Matsumoto, S.;
Tamaru, Y. Angew. Chem., Int. Ed. 1999, 38, 397. (d) Kimura, M.;
Shibata, K.; Koudahashi, Y.; Tamaru, Y. Tetrahedron Lett. 2000, 41,
6789. (e) Kimura, M.; Ezoe, A.; Tanaka, S.; Tamaru, Y. Angew. Chem.,
Int. Ed. 2001, 40, 3600. (f) Loh, T.-P.; Song, H.-Y.; Zhou, Y. Org. Lett.
2002, 4, 2715. (g) Sato, Y.; Sawaki, R.; Saito, N.; Mori, M. J. Org. Chem.
2002, 67, 656. (h) Kimura, M.; Ezoe, A.; Mori, M.; Iwata, K.; Tamaru,
Y. J. Am. Chem. Soc. 2006, 128, 8559. (i) Yang, Y.; Zhu, S.-F.; Duan,
H.-F.; Zhou, C.-Y.; Wang, L.-X.; Zhou, Q.-L. J. Am. Chem. Soc. 2007,
129, 2248. (j) Sato, Y.; Hinata, Y.; Seki, R.; Oonishi, Y.; Saito, N. Org.
(1) For selected reviews on C-C bond forming hydrogenation and
transfer hydrogenation, see: (a) Bower, J. F.; Krische, M. J. Top.
Organomet. Chem. 2011, 43, 107. (b) Hassan, A.; Krische, M. J. Org.
Proc. Res. Devel. 2011, 15, 1236. (c) Moran, J.; Krische, M. J. Pure Appl.
Chem. 2012, 84, 1729.
(2) For a review on the topic of redox economy, see: Baran, P. S.;
Hoffmann, R. W.; Burns, N. Z. Angew. Chem., Int. Ed. 2009, 48, 2854.
(3) For iridium catalyzed transfer hydrogenative coupling of alcohols
to dienes, see: (a) Bower, J. F.; Patman, R. L.; Krische, M. J. Org. Lett.
2008, 10, 1033. (b) Zbieg, J. R.; Fukuzumi, T.; Krische, M. J. Adv. Synth.
Catal. 2010, 352, 2416.
(4) For ruthenium catalyzed transfer hydrogenative coupling of
alcohols to dienes, see : (a) Shibahara, F.; Bower, J. F.; Krische, M. J.
J. Am. Chem. Soc. 2008, 130, 6338. (b) Han, H.; Krische, M. J. Org. Lett.
2010, 12, 2844. (c) Zbieg, J. R.; Moran, J.; Krische, M. J. J. Am. Chem.
Soc. 2011, 133, 10582. (d) Zbieg, J. R.; Yamaguchi, E.; McInturff, E. L.;
Krische, M. J. Science 2012, 336, 324. (e) Leung, J. C.; Geary, L. M.;
Chen, T.-Y.; Zbieg, J. R.; Krische, M. J. J. Am. Chem. Soc. 2012, 134,
15700. (f) Geary, L. M.; Glasspoole, B. W.; Kim, M. M.; Krische, M. J.
J. Am. Chem. Soc. 2013, 134, 3796Also, see reference 5.
€
Lett. 2007, 9, 5597. (k) Kopfer, A.; Sam, B.; Breit, B.; Krische, M. J.
Chem. Sci. 2013, 4, 1876.
r
10.1021/ol401184k
XXXX American Chemical Society