Journal of the American Chemical Society
Communication
(d) Lumbroso, A.; Cooke, M. L.; Breit, B. Angew. Chem., Int. Ed. 2013,
52, 1890.
(2) For reviews of Ni-catalyzed alkyne−carbonyl reductive coupling,
see: (a) Montgomery, J.; Sormunen, G. J. Top. Curr. Chem. 2007, 279,
1. (b) Moslin, R. M.; Miller-Moslin, K.; Jamison, T. F. Chem. Commun.
2007, 4441.
intermediates: (a) Webb, N. J.; Marsden, S. P.; Raw, S. A. Org. Lett.
2014, 16, 4718. (b) Moselage, M.; Sauermann, N.; Richter, S. C.;
Ackermann, L. Angew. Chem., Int. Ed. 2015, 54, 6352.
(9) For ruthenium(0)-catalyzed C−C coupling of vicinally
dioxygenated secondary alcohols with 1,3-dienes, see: (a) Leung, J.
C.; Geary, L. M.; Chen, T.-Y.; Zbieg, J. R.; Krische, M. J. J. Am. Chem.
Soc. 2012, 134, 15700. (b) Chen, T.-Y.; Krische, M. J. Org. Lett. 2013,
15, 2994. (c) Geary, L. M.; Glasspoole, B. W.; Kim, M. M.; Krische, M.
J. J. Am. Chem. Soc. 2013, 135, 3796. (d) Park, B. Y.; Montgomery, T.
P.; Garza, V. J.; Krische, M. J. J. Am. Chem. Soc. 2013, 135, 16320.
(e) Geary, L. M.; Chen, T.-Y.; Montgomery, T. P.; Krische, M. J. J.
Am. Chem. Soc. 2014, 136, 5920. (f) Kasun, Z. A.; Geary, L. M.;
Krische, M. J. Chem. Commun. 2014, 7545.
(10) For Ru3(CO)12-catalyzed Pauson−Khand-type reactions, see:
(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.
(3) For reviews on rhodium- and iridium-catalyzed alkyne−carbonyl
reductive coupling via hydrogenation, see: (a) Patman, R. L.; Bower, J.
F.; Kim, I. S.; Krische, M. J. Aldrichimica Acta 2008, 41, 95.
(b) Hassan, A.; Krische, M. J. Org. Proc. Res. Devel. 2011, 15, 1236.
(c) Bower, J. F.; Krische, M. J. Top. Organomet. Chem. 2011, 34, 107.
(4) For metal-catalyzed alkyne−alcohol redox-neutral carbonyl
vinylation, see: (a) Patman, R. L.; Chaulagain, M. R.; Williams, V.
M.; Krische, M. J. J. Am. Chem. Soc. 2009, 131, 2066. (b) McInturff, E.
L.; Nguyen, K. D.; Krische, M. J. Angew. Chem., Int. Ed. 2014, 53, 3232.
(c) Nakai, K.; Yoshida, Y.; Kurahashi, T.; Matsubara, S. J. Am. Chem.
Soc. 2014, 136, 7797.
(5) Reductive coupling of acetylene to carbonyl and imine partners
under the conditions of rhodium-catalyzed hydrogenation to deliver
products of (Z)-butadienylation: (a) Kong, J. R.; Krische, M. J. J. Am.
Chem. Soc. 2006, 128, 16040. (b) Skucas, E.; Kong, J. R.; Krische, M. J.
J. Am. Chem. Soc. 2007, 129, 7242. (c) Han, S. B.; Kong, J. R.; Krische,
M. J. Org. Lett. 2008, 10, 4133. (d) Williams, V. M.; Kong, J. R.; Ko, B.
J.; Mantri, Y.; Brodbelt, J. S.; Baik, M.-H.; Krische, M. J. J. Am. Chem.
Soc. 2009, 131, 16054.
(6) For stoichiometric fragmentation of zirconium-based metalla-
cycles, see: (a) Knight, K. S.; Waymouth, R. M. Organometallics 1994,
13, 2575. (b) Takahashi, T.; Kondakov, D. Y.; Suzuki, N.
Organometallics 1994, 13, 3411. (c) Takahashi, T.; Kondakov, D. Y.;
Xi, Z.; Suzuki, N. J. Am. Chem. Soc. 1995, 117, 5871. (d) Bird, A. J.;
Taylor, R. J. K.; Wei, X. Synlett 1995, 1237. (e) Millward, D. B.;
Waymouth, R. M. Organometallics 1997, 16, 1153. (f) Takahashi, T.;
Xi, Z.; Fischer, R.; Huo, S.; Xi, C.; Nakajima, K. J. Am. Chem. Soc.
1997, 119, 4561. (g) Kotora, M.; Gao, G.; Li, Z.; Xi, Z.; Takahashi, T.
Tetrahedron Lett. 2000, 41, 7905. (h) Hara, R.; Ura, Y.; Huo, S.; Kasai,
K.; Suzuki, N.; Takahashi, T. Inorg. Chim. Acta 2000, 300−302, 741.
(i) Liu, Y.; Zhong, Z.; Nakajima, K.; Takahashi, T. J. Org. Chem. 2002,
67, 7451. (j) Chinkov, N.; Chechik, H.; Majumdar, S.; Liard, A.;
(11) For a recent review of osmium-catalyzed hydrogenation and
transfer hydrogenation, see: Chelucci, G.; Baldino, S.; Baratta, W. Acc.
Chem. Res. 2015, 48, 363.
(12) π-Backbonding between the enol carboxylate and metal catalyst,
as described by the Dewar−Chatt−Duncanson model, facilitates
oxidative coupling to the transient activated ketone by conferring
nucleophilic character to the bound enol carboxylate. Due to
relativistic effects, osmium is a stronger π-donor than ruthenium
[MHCl(CO)(PPh3)3, M = Os, νCO = 1906 cm−1; M = Ru, νCO = 1922
cm−1]: Parshall, G. W. Complexes of Ruthenium, Osmium, Rhodium,
and Iridium Containing Hydride Carbonyl, or Nitrosyl Ligands. In
Inorganic Syntheses; Ahmad, N., Levison, J. J., Robinson, S. D., Uttley,
M. F., Eds.; McGraw-Hill, Inc.: New York, 1974; Vol. 15, pp 45−64.
This may account for the enhanced performance of osmium-based
catalysts in processes that involve the oxidative coupling of reactants
that embody higher lying LUMOs.
(13) McInturff, E. L.; Mowat, J.; Waldeck, A. R.; Krische, M. J. J. Am.
Chem. Soc. 2013, 135, 17230.
Marek, I. Synthesis 2002, 2473. (k) Barluenga, J.; Rodríguez, F.;
́
Alvarez-Rodrigo, L.; Fananas
́
, F. J. Chem.Eur. J. 2004, 10, 101.
̃
́
(l) Barluenga, J.; Rodriguez, F.; Alvarez-Rodrigo, L.; Zapico, J. M.;
Fananas
Rodrigo, L.; Rodriguez, F.; Fananas
43, 3932. (n) Owen, D. R.; Whitby, R. J. Synthesis 2005, 2061.
́
́
, F. J. Chem.Eur. J. 2004, 10, 109. (m) Barluenga, J.; Alvarez-
̃
́
, F. J. Angew. Chem., Int. Ed. 2004,
̃
́
Reviews: (o) Barluenga, J.; Rodríguez, F.; Alvarez-Rodrigo, L.;
Fananas
́
, F. J. Chem. Soc. Rev. 2005, 34, 762. (p) Fananas
́
, F. J.;
̃
̃
Rodríguez, F. Eur. J. Org. Chem. 2008, 1315.
(7) For stoichiometric fragmentation of titanium-based metallacycles,
see: (a) Takayama, Y.; Gao, Y.; Sato, F. Angew. Chem., Int. Ed. Engl.
1997, 36, 851. (b) Takayama, Y.; Okamoto, S.; Sato, F. Tetrahedron
Lett. 1997, 38, 8351. (c) Yamazaki, T.; Urabe, H.; Sato, F. Tetrahedron
Lett. 1998, 39, 7333. (d) Takayama, Y.; Okamoto, S.; Sato, F. J. Am.
Chem. Soc. 1999, 121, 3559. (e) Okamoto, S.; Takayama, Y.; Gao, Y.;
Sato, F. Synthesis 2000, 975. (f) Campbell, A. D.; Raynham, T. M.;
Taylor, R. J. K. J. Chem. Soc., Perkin Trans. 1 2000, 3194. (g) Delas, C.;
Urabe, H.; Sato, F. Tetrahedron Lett. 2001, 42, 4147. (h) Nakajima, R.;
Urabe, H.; Sato, F. Chem. Lett. 2002, 4. (i) Tanaka, R.; Sasaki, M.;
Sato, F.; Urabe, H. Tetrahedron Lett. 2005, 46, 329. (j) Takeda, T.;
Arai, K.; Shimokawa, H.; Tsubouchi, A. Tetrahedron Lett. 2005, 46,
775. (k) Ogata, A.; Nemeto, M.; Arai, K.; Kobayashi, K.; Tsubouchi,
A.; Takeda, T. Eur. J. Org. Chem. 2006, 878. (l) Ogata, A.; Nemoto,
M.; Kobayashi, K.; Tsubouchi, A.; Takeda, T. J. Org. Chem. 2007, 72,
3816. (m) Oishi, S.; Hatano, K.; Tsubouchi, A.; Takeda, T. Chem.
Commun. 2011, 47, 11639. (n) Cheng, X.; Micalizio, G. C. Org. Lett.
2014, 16, 5144.
(8) Late transition metal-catalyzed couplings of vinyl acetates and
related enol derivatives to aryl C−H compounds are postulated to
occur through ortho-directed C−H metalation−migratory insertion
pathways rather than oxidative coupling to form metallacyclic
D
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX