(f) K. Suda, T. Kikkawa, S.-i. Nakajima and T. Takanami, J. Am. Chem.
Soc., 2004, 126, 9554.
Compared to α-chloroester (4b), we found that α-bromoesters
(4a, 4c–4e) yielded epoxides with higher yields, because of the
higher leaving ability of Br atom compared with Cl. For α-halo-
carbonyl chloride, the yield was very poor (Table 2, entry 6).
Even when we tried to decrease the reaction temperature, the
yield was still not improved. Finally, a special substrate—con-
taining two α-bromoester groups—didn’t yield the correspond-
ing diallylic epoxide, but 5e was obtained in acceptable yield.
In summary, a new method was developed to produce allylic
and diallylic epoxides in mild conditions with good yields.
Further studies are under way to expand a series of organomag-
nesium reagents which can react with α-haloketones and esters.
4 (a) O. D. Pavel, B. Cojocaru, E. Angelescu and V. I. Parvulescu, Appl.
Catal., A: Gen., 2011, 403, 83; (b) H.-K. Kwong, P.-K. Lo, K.-C. Lau
and T.-C. Lau, Chem. Commun., 2011, 47, 4273; (c) F. Romano,
A. Linden, M. Mba, C. Zonta and G. Licini, Adv. Synth. Catal., 2010,
352, 2937; (d) Y. Liu, H. J. Zhang, Y. Lu, Y. Q. Cai and X. L. Liu, Green
Chem., 2007, 9, 1114; (e) J. L. Zhang, H. B. Zhou, J. S. Huang and C.
M. Che, Chem.–Eur. J., 2002, 8, 1554.
5 (a) A. S. Demir, M. Emrullahoglu, E. Pirkin and N. Akca, J. Org. Chem.,
2008, 73, 8992; (b) A. Fustner, J. Organomet. Chem., 1987, 336, C33;
(c) M. Makosza and I. V. Krylova, Eur. J. Org. Chem., 1998, 2229;
(d) J. M. Concellon, C. Concellon and P. Diaz, Eur. J. Org. Chem., 2006,
2197.
6 (a) I. Shibata, S. Fukuoka and A. Baba, Chem. Lett., 1998, 533;
(b) K. Yano, Y. Hatta, A. Baba and H. Matsuda, Synthesis, 1992, 693;
(c) M. Yasuda, T. Oh-Hata, I. Shibata, A. Baba, H. Matsuda and
N. Sonoda, Bull. Chem. Soc. Jpn., 1995, 68, 1180; (d) I. Pri-Bar, P.
S. Pearlman and J. K. Stille, J. Org. Chem., 1983, 48, 4629; (e) K. Yano,
Y. Hatta, A. Baba and H. Matsuda, Synlett, 1991, 555; (f) M. Kosugi,
H. Arai, A. Yoshino and T. Migita, Chem. Lett., 1978, 795.
7 (a) J. J. Song, Z. Tan, J. Xu, J. T. Reeves, N. K. Yee, R. Ramdas,
F. Gallou, K. Kuzmich, L. DeLattre, H. Lee, X. Feng and C.
H. Senanayake, J. Org. Chem., 2007, 72, 292; (b) J. Amaudrut and
O. Wiest, Org. Lett., 2000, 2, 1251; (c) D. C. Forbes, M. C. Standen and
D. L. Lewis, Org. Lett., 2003, 5, 2283; (d) J. K. Crandall, H. S. Magaha,
M. A. Henderson, R. K. Widener and G. A. Tharp, J. Org. Chem., 1982,
47, 5372; (e) V. Mark, J. Am. Chem. Soc., 1963, 85, 1884;
(f) M. Klawonn, S. Bhor, G. Mehltretter, C. Döbler, C. Fischer and
M. Beller, Adv. Synth. Catal., 2003, 345, 389; (g) G. Lemonnier,
L. Zoute, J. C. Quirion and P. Jubault, Org. Lett., 2010, 12, 844.
8 (a) R. V. Ottenbacher, K. P. Bryliakov and E. P. Talsi, Adv. Synth. Catal.,
2011, 353, 885; (b) W. S. Liu, R. Zhang, J. S. Huang, C. M. Che and
S. M. Peng, J. Org. Chem., 2001, 634, 34; (c) B. S. Lane and
K. Burgess, Chem. Rev., 2003, 103, 2457; (d) R. D. Bach, C. Canepa,
J. E. Winter and P. E. Blanchette, J. Org. Chem., 1997, 62, 5191.
9 M. Zhang, Y. Y. Hu and S. L. Zhang, Chem.–Eur. J., 2009, 15, 10732.
10 J. Pan, M. Zhang and S. L. Zhang, Org. Biomol. Chem., 2012, 10, 1060.
11 N. G. Gaylord and E. I. Becker, Chem. Rev., 1951, 49, 413.
12 (a) L. Henry, Comptes Rendus Chimie, 1906, 142, 1023; (b) L. Henry,
Comptes Rendus Chimie, 1907, 144, 308; (c) L. Henry, Comptes Rendus
Chimie, 1907, 145, 21; (d) S. Sato, I. Matsuda and Y. Izumi, J. Organo-
met. Chem., 1989, 359, 255; (e) S. Sato, I. Matsuda and Y. Izumi, Tetra-
hedron Lett., 1985, 26, 1527; (f) B. M. Trost, W. Tang and J. L. Schulte,
Org. Lett., 2000, 2, 4013; (g) M. S. Newman and M. D. Farbman, J. Am.
Chem. Soc., 1944, 66, 1550; (h) T. A. Geissman and R. I. Akawie, J. Am.
Chem. Soc., 1951, 73, 1993; (i) F. H. Norton and H. B. Hass, J. Am.
Chem. Soc., 1936, 58, 2147.
Acknowledgements
We gratefully acknowledge A Project Funded by the Priority
Academic Program Development of Jiangsu Higher Education
Institutions, the National Natural Science Foundation of China
(No. 21072143) for financial support.
Notes and references
1 (a) K. A. Jorgensen, Chem. Rev., 1989, 89, 431; (b) A. S. Rao, in Com-
prehensive Organic Synthesis, ed. B. M. Trost and I. Fleming, Pergamon
Press, Oxford, U.K., 1991, vol. 7, p. 357; (c) M. Hudlucky, Oxidations in
Organic Chemistry, ACS Monograph Series, American Chemical Society,
Washington DC, 1990; (d) M. W. C. Robinson, K. S. Pillinger,
I. Mabbett, D. A. Timms and A. E. Graham, Tetrahedron, 2010, 66,
8377; (e) O. A. Wong and Y. Shi, Chem. Rev., 2008, 108, 3958;
(f) M. W. C. Robinson, A. M. Davies, R. Buckle, I. Mabbett, S.
H. Taylor and A. E. Graham, Org. Biomol. Chem., 2009, 7, 2559; (g) G.
X. Jiang, J. Chen, H. Y. Thu, J. S. Huang, N. Y. Zhu and C. M. Che,
Angew. Chem., Int. Ed., 2008, 47, 6638.
2 (a) J. Smith, Synthesis, 1984, 629; (b) A. Padwa and S. S. Murphree,
ARKIVOC, 2006, 3, 6; (c) H. Cavdar and N. Saracoglu, Eur. J. Org.
Chem., 2008, 4615.
3 (a) S. Kulasegaram and R. J. Kulawiec, J. Org. Chem., 1994, 59, 7195;
(b) C. Lemini, M. Ordonez, J. Perez-Flores and R. Cruz-Almanza, Synth.
Commun., 1995, 25, 2695; (c) J. Picions, S. J. Mahmood, A. Gill,
M. Hilliard and M. M. Hossain, Tetrahedron Lett., 1998, 39, 2681; (d) B.
C. Ranu and U. Jana, J. Org. Chem., 1998, 63, 8212; (e) Y. D. Vankar,
N. C. Chaudhuri and S. P. Singh, Synth. Commun., 1986, 16, 1621;
3184 | Org. Biomol. Chem., 2012, 10, 3182–3184
This journal is © The Royal Society of Chemistry 2012