Journal of the American Chemical Society
Communication
(8) Examples with CO and isocyanates: (a) Getzler, Y. D. Y. L.;
Mahadevan, V.; Lobkovsky, E. B.; Coates, G. W. J. Am. Chem. Soc.
2002, 124, 1174−1175. (b) Mahadevan, V.; Getzler, Y. D. Y. L.;
Coates, G. W. Angew. Chem., Int. Ed. 2002, 41, 2781−2784.
(c) Kramer, J. W.; Lobkovsky, E. B.; Coates, G. W. Org. Lett. 2006,
8, 3709−3712. (d) Church, T. L.; Byrne, C. M.; Lobkovsky, E. B.;
Coates, G. W. J. Am. Chem. Soc. 2007, 129, 8156−8162.
(9) The coupling of vinyl epoxides with a variety of nucleophiles via
allylmetal intermediates is well developed. See (a) Muzart, J. Eur. J.
Org. Chem. 2011, 4717−4741. (b) Trost, B. M.; Molander, G. A. J. Am.
Chem. Soc. 1981, 103, 5969−5972. (c) Tsuji, J.; Kataoka, H.;
Kobayashi, Y. Tetrahedron Lett. 1981, 22, 2575−2578.
(26) (a) Hirao, T. Top. Curr. Chem. 2007, 279, 53−75. (b) Gansauer,
̈
A. Chem. Commun. 1997, 457−458.
(27) (a) Ford, L.; Jahn, U. Angew. Chem., Int. Ed. 2009, 48, 6386−
6389. (b) Jahn, U. Radicals in Transition Metal Catalyzed Reactions?
Transition Metal Catalyzed Radical Reactions? A Fruitful Interplay
Anyway, Parts I-III. In Radicals in Synthesis III; Heinrich, M.; Gansauer,
̈
A., Eds.; Springer: Berlin Heidelberg: 2012; Vol. 320, pp 191−451.
(10) Nielsen, D. K.; Doyle, A. G. Angew. Chem., Int. Ed. 2011, 50,
6056−6059.
(11) (a) Jiang, N.; Hu, Q.; Reid, C. S.; Lu, Y.; Li, C.-J. Chem.
Commun. 2003, 2318−2319. (b) Roy, U. K.; Roy, S. Tetrahedron 2006,
62, 678−683.
(12) (a) Gansauer, A.; Narayan, S. Adv. Synth. Catal. 2002, 344, 465−
̈
475. (b) RajanBabu, T. V.; Nugent, W. A. J. Am. Chem. Soc. 1988, 110,
8561−8562. (c) RajanBabu, T. V.; Nugent, W. A. J. Am. Chem. Soc.
1994, 116, 986−997. (d) Gansauer, A.; Barchuk, A.; Keller, F.;
̈
Schmitt, M.; Grimme, S.; Gerenkamp, M.; Muck-Lichtenfeld, C.;
̈
Daasbjerg, K.; Svith, H. J. Am. Chem. Soc. 2007, 129, 1359−1371.
(e) Gansauer, A.; Fleckhaus, A.; Lafont, M. A.; Okkel, A.; Kotsis, K.;
Anoop, A.; Neese, F. J. Am. Chem. Soc. 2009, 131, 16989−16999.
(f) Gansauer, A.; Shi, L.; Otte, M. J. Am. Chem. Soc. 2010, 132,
̈
̈
11858−11859. (g) Gansauer, A.; Fan, C.-A.; Keller, F.; Karbaum, P.
̈
Chem.Eur. J. 2007, 13, 8084−8090.
(13) Gansauer, A.; Behlendorf, M.; von Laufenberg, D.; Fleckhaus,
̈
A.; Kube, C.; Sadasivam, D. V.; Flowers, R. A. Angew. Chem., Int. Ed.
2012, 51, 4739−4742.
(14) (a) Everson, D. A.; Shrestha, R.; Weix, D. J. J. Am. Chem. Soc.
2010, 132, 920−921. (b) Everson, D. A.; Jones, B. A.; Weix, D. J. J.
Am. Chem. Soc. 2012, 134, 6146−6159. (c) Everson, D. A.; George, D.
T.; Weix, D. J.; Buergler, J. F.; Wood, J. L. Org. Synth. 2013, 90, 200−
214.
(15) Biswas, S.; Weix, D. J. J. Am. Chem. Soc. 2013, 135, 16192−
16197.
(16) See also Hu’s reaction of [NiII](Alkyl) with an alkyl radical to
form cross product: Breitenfeld, J.; Ruiz, J.; Wodrich, M. D.; Hu, X. J.
Am. Chem. Soc. 2013, 135, 12004−12012.
(17) Oshima invoked a bromohydrin in reactions with styrenes.5
(18) (a) Chini, M.; Crotti, P.; Gardelli, C.; Macchia, F. Tetrahedron
1992, 48, 3805. (b) Soroka, M.; Goldeman, W. Tetrahedron 2005, 61,
4233. (c) Mathieu-Pelta, I.; Evans, S. A. J. Org. Chem. 1992, 57, 3409.
(d) Eisch, J. J.; Liu, Z. R.; Ma, X.; Zheng, G. X. J. Org. Chem. 1992, 57,
5140−5144. (e) Bonini, C.; Righi, G. Synthesis 1994, 1994, 225−238.
(19) Coupling of these intermediates with metal hydrides is known:
(a) Gansauer, A.; Fan, C.; Piestert, F. J. Am. Chem. Soc. 2008, 130,
̈
6916−6917. (b) Gansauer, A.; Otte, M.; Shi, L. J. Am. Chem. Soc.
̈
2011, 133, 416−417.
(20) (a) Kolthoff, I. M.; Chantooni, M. K.; Bhowmik, S. J. Am. Chem.
́
Soc. 1968, 90, 23−28. (b) Benoit, R. L.; Lefebvre, D.; Frechette, M.
Can. J. Chem. 1987, 65, 996−1001. (c) Bordwell, F. G. Acc. Chem. Res.
1988, 21, 456−463.
(21) Miyashita, A.; Shimada, T.; Sugawara, A.; Nohira, H. Chem. Lett.
1986, 15, 1323−1326.
(22) Kuroboshi, M.; Tanaka, M.; Kishimoto, S.; Goto, K.; Mochizuki,
M.; Tanaka, H. Tetrahedron Lett. 2000, 41, 81−84.
(23) Schadt, F. L.; Lancelot, C. J.; Schleyer, P. v. R. J. Am. Chem. Soc.
1978, 100, 228−246.
(24) Although TiIVX4 has been reported to form halohydrins from
internal attack,18d,e the conditions were different (hydrocarbon solvent,
low temperature, slow addition of epoxide), and the formation of
Cp2TiIIICl is evident from the color change of the reaction (dark red to
olive green).
(25) Matsumoto, T.; Ishida, T.; Yoshida, T.; Terao, H.; Takeda, Y.;
Asakawa, Y. Chem. Pharm. Bull. 1992, 40, 1721−1726.
D
dx.doi.org/10.1021/ja410704d | J. Am. Chem. Soc. XXXX, XXX, XXX−XXX