reported pioneering studies involving a CÀH oxidative
reaction based on in situ generated ammonium hypoiodite
species using either H2O2 or TBHP as the oxidant.18 The CÀH
oxidation reaction worked well in the presence of stoichio-
metric amounts of Bu4NOH and iodine (in situ generation of
[Bu4N]+[IO]À).19 In sharp contrast, the existence of ammo-
nium hypoiodite halted the present aldehyde CÀH oxidation
(Scheme 2b). Although not conclusive, we currently believe
that hypoiodite is not the actual catalytic species in the
aldehydes CÀH oxidation reaction.
(b) S. N. Gupta, I. Gupta and D. C. Neckers, J. Polym. Sci.,
Polym. Chem. Ed., 1981, 19, 103; (c) L. Wang, X. Liu and Y. Li,
Macromolecules, 1998, 31, 3446.
8 (a) P. C. Montevecchi, A. Manetto, M. L. Navacchia and
C. Chatgilialoglu, Tetrahedron, 2004, 60, 4303; (b) S. Antonello,
M. Crisma, F. Formaggio, A. Moretto, F. Taddei, C. Toniolo and
F. Maran, J. Am. Chem. Soc., 2002, 124, 11503; (c) B. K. Shah and
D. C. Neckers, J. Am. Chem. Soc., 2004, 126, 1830.
9 (a) F. Formaggio, M. Crisma, L. Scipionato, S. Antonello,
F. Maran and C. Toniolo, Org. Lett., 2004, 6, 2753; (b) Y. Li,
S. Niu, B. Sun, S. Liu, X. Liu and Y. Che, Org. Lett., 2010, 12, 3144.
10 (a) D. A. Powell and H. Fan, J. Org. Chem., 2010, 75, 2726;
(b) G. Pelletier and D. A. Powell, Org. Lett., 2006, 8, 6031.
11 (a) M. S. Kharasch, G. Sosnovsky and N. C. Yang, J. Am. Chem.
Soc., 1959, 81, 5819; For reviews, see: (b) M. B. Andrus and
J. C. Lashley, Tetrahedron, 2002, 58, 845; (c) J. Eames and
M. Watkinson, Angew. Chem., Int. Ed., 2001, 40, 3567; For
selected examples, see: (d) A. V. Malkov, M. Bella, V. Langer
In summary, a Bu4NI-catalyzed CÀH oxidation of aldehydes
has been developed. This process represents the first synthesis of
tert-butyl peresters directly from aldehydes and TBHP. Most
importantly, the practicality of the method, as well as its combi-
nation with the KharaschÀSosnovsky reaction, renders it suitable
for applications in synthetic chemistry. Based on the control
experiments, a radical process was proposed in the catalytic cycle.
Investigations that provide a more detailed mechanism and
further applications are ongoing in our laboratory.
and P. Kocovsky´ , Org. Lett., 2000, 2, 3047; (e) M. B. Andrus and
Z. Zhou, J. Am. Chem. Soc., 2002, 124, 8806; (f) A. S. Gokhale,
A. B. E. Minidis and A. Pfaltz, Tetrahedron Lett., 1995, 36, 1831;
(g) M. T. Rispens, C. Zondercu and B. L. Feringa, Tetrahedron:
Asymmetry, 1995, 6, 661; (h) Y. Kohmura and T. Katsuki, Tetra-
hedron Lett., 2000, 41, 3941.
12 (a) N. Milas and D. M. Surgenor, J. Am. Chem. Soc., 1946, 68, 642;
(b) S. L. Silbert and D. Swern, J. Am. Chem. Soc., 1959, 81, 2364;
(c) N. A. Milas, D. G. Orphanos and R. J. Klein, J. Org. Chem.,
1964, 29, 3099; (d) M. Y. Lu, R. Bao, W. Liu and Y. Li, J. Org.
Chem., 1995, 60, 5341; (e) Y. Hamada, A. Mizuno, T. Ohno and
T. Shioiri, Chem. Pharm. Bull., 1984, 32, 3683.
13 Recently, Li et al. reported a three-component reaction of alkenes,
aldehydes, and TBHP catalyzed by FeCl2, see: W. Liu, Y. Li,
K. Liu and Z. Li, J. Am. Chem. Soc., 2011, 133, 10756.
A Project Funded by the Priority Academic Program
Development of Jiangsu Higher Education Institutions
(PAPD) and NSFC (20802047, 21072142).
Notes and references
1 For reviews, see: (a) Y. J. Park, J.-W. Park and C.-H. Jun, Acc.
Chem. Res., 2008, 41, 222; (b) M. C. Willis, Chem. Rev., 2010,
110, 725.
14 Recently, several groups described transition-metal-catalyzed C–H
oxidation for allylic ester, see: (a) H. Grennberg and J.-E. Backvall,
2 For representative examples of aldehydes CÀH activation, see:
(a) C.-H. Jun, H. Lee, J.-B. Hong and B.-I. Kwon, Angew. Chem.,
Int. Ed., 2002, 41, 2146; (b) M. Pucheault, S. Darses and
J.-P. Genet, J. Am. Chem. Soc., 2004, 126, 15356; (c) K. Kundu,
J. V. McCullagh and A. T. Morehead, Jr., J. Am. Chem. Soc.,
2005, 127, 16042; (d) A. Chan and K. A. Scheidt, J. Am. Chem.
Soc., 2006, 128, 4558; (e) R. T. Stemmler and C. Bolm, Adv. Synth.
Catal., 2007, 349, 1185; (f) A. H. Roy, C. P. Lenges and
M. Brookhart, J. Am. Chem. Soc., 2007, 129, 2082;
(g) F. Shibahara, J. F. Bower and M. J. Krische, J. Am. Chem.
Soc., 2008, 130, 14120; (h) J. D. Osborne, H. E. Randell-Sly,
G. S. Currie, A. R. Cowley and M. C. Willis, J. Am. Chem. Soc.,
2008, 130, 17232; (i) Z. Shen, H. A. Khan and V. M. Dong, J. Am.
Chem. Soc., 2008, 130, 2916; (j) Y. Shibata and K. Tanaka, J. Am.
Chem. Soc., 2009, 131, 12552; (k) H. Taniguchi, T. Ohmura and
M. Suginome, J. Am. Chem. Soc., 2009, 131, 11298; (l) K. Hirano,
A. T. Biju, I. Piel and F. Glorius, J. Am. Chem. Soc., 2009,
131, 14190; (m) A. T. Biju, N. E. Wurz and F. Glorius, J. Am.
Chem. Soc., 2010, 132, 5970; (n) Y. Kuninobu, T. Matsuki and
K. Takai, Org. Lett., 2010, 12, 2948; (o) M. M. Coulter, K. G. M.
Kou, B. Galligan and V. M. Dong, J. Am. Chem. Soc., 2010,
132, 16330; (p) X. Bugaut, F. Liu and F. Glorius, J. Am. Chem.
Soc., 2011, 133, 8130; (q) V. Chudasama, R. J. Fitzmaurice and
S. Caddick, Nat. Chem., 2010, 2, 592; (r) V. Chudasama,
J. M. Ahern, D. V. Dhokia, R. J. Fitzmaurice and S. Caddick,
¨
Chem.–Eur. J., 1998, 4, 1083; (b) M. S. Chen and M. C. White,
J. Am. Chem. Soc., 2004, 126, 1346; (c) M. S. Chen, N. Prabagaran,
N. A. Labenz and M. C. White, J. Am. Chem. Soc., 2005, 127, 6970;
(d) L. T. Pilarski, N. Selander, D. Bose and K. J. Szabo, Org. Lett.,
´
¨
2009, 11, 5518; (e) E. M. Stang and M. C. White, Nat. Chem., 2009,
1, 547; (f) E. Thiery, C. Aouf, J. Belloy, D. Harakat, J. Le Bras and
J. Muzart, J. Org. Chem., 2010, 75, 1771; (g) W. H. Henderson,
C. T. Check, N. Proust and J. P. Stambuli, Org. Lett., 2010, 12, 824;
(h) A. N. Campbell, P. B. White, I. A. Guzei and S. S. Stahl, J. Am.
Chem. Soc., 2010, 132, 15116; (i) G. Yin, Y. Wu and G. Liu, J. Am.
Chem. Soc., 2010, 132, 11978; (j) A. Lumbroso, P. Koschker,
N. R. Vautravers and B. Breit, J. Am. Chem. Soc., 2011,
133, 2386; For review, see: (k) H. Li, B.-J. Li and Z.-J. Shi, Catal.
Sci. Technol., 2011, 1, 191 and references therein.
15 When the reactions were conducted under the optimized condi-
tions (water as solvent), lower yields were observed due to the poor
solubility of alkenes.
16 The generation of tert-butoxyl and tert-butylperoxy radical via a
SET process, see: (a) M. S. Kharasch, P. Pauson and
W. Nudenberg, J. Org. Chem., 1953, 18, 322; (b) D. H. R.
Barton, V. N. Le Gloahec, H. Patin and F. Launay, New J. Chem.,
1998, 22, 559; (c) L. Gan, S. Huang, X. Zhang, A. Zhang,
B. Cheng, H. Cheng, X. Li and G. Shang, J. Am. Chem. Soc.,
2002, 124, 13384; (d) C. M. Jones and M. J. Burkitt, J. Am. Chem.
Soc., 2003, 125, 6946; (e) E. C. McLaughlin, H. Choi, K. Wang,
G. Chiou and M. P. Doyle, J. Org. Chem., 2009, 74, 730.
17 The generation of acyl radicals directly from aldehydes, see:
(a) G. A. DiLabio, K. U. Ingold, M. D. Roydhouse and
J. C. Walton, Org. Lett., 2004, 6, 4319; (b) R. Shelkov and
A. Melman, Eur. J. Org. Chem., 2005, 1397; (c) M. Conte,
H. Miyamura, S. Kobayashi and V. Chechik, Chem. Commun.,
2010, 46, 145; (d) J. M. Pruet, J. D. Robertus and E. V. Anslyn,
Tetrahedron Lett., 2010, 51, 2539.
Chem. Commun., 2011, 47, 3269; (s) O. Basle, J. Bidange, Q. Shuai
´
and C.-J. Li, Adv. Synth. Catal., 2010, 352, 1145.
3 Recently, we and others developed Bu4NI-catalyzed C–H activa-
tion using TBHP, see: (a) L. Chen, E. Shi, Z. Liu, S. Chen, W. Wei,
H. Li, K. Xu and X. Wan, Chem.–Eur. J., 2011, 17, 4085;
(b) M. Uyanik, D. Suzuki, T. Yasui and K. Ishihara, Angew.
Chem., Int. Ed., 2011, 50, 5331; (c) T. Froehr, C. P. Sindlinger,
U. Kloeckner, P. Finkbeiner and B. J. Nachtsheim, Org. Lett.,
2011, 13, 3754.
4 Caution: tert-butyl peresters are potentially explosive.
5 For reviews on the CDC reaction, see: (a) C.-J. Li, Acc. Chem.
Res., 2009, 42, 335; (b) C. S. Yeung and V. M. Dong, Chem. Rev.,
2011, 111, 1215.
6 W. Ando, Organic Peroxides, Wiley-Interscience, New York, 1992.
7 (a) E. T. Denisov, T. G. Denisova and T. S. Pokidova, Handbook
of free radical initiators, Wiley-Interscience, New Jersey, 2003;
18 (a) M. Uyanik, H. Okamoto, T. Yasui and K. Ishihara, Science,
2010, 328, 1376; (b) see ref. 3b.
19 For oxidation using in situ generated hypoiodite, see:
(a) S. Yamada, D. Morizono and K. Yamamoto, Tetrahedron
Lett., 1992, 33, 4329; (b) M. Kirihara, Y. Asai, S. Ogawa,
T. Noguchi, A. Hatano and Y. Hirai, Synthesis, 2007, 3286;
(c) ref. 18 and references therein.
c
This journal is The Royal Society of Chemistry 2011
Chem. Commun., 2011, 47, 10827–10829 10829