Page 5 of 6
Journal of the American Chemical Society
6. (a) Leibeling, M.; Shurrush, K. A.; Werner, V.; Perrin, L.; Marek,
I. Angew. Chem., Int. Ed. 2016, 55, 6057. (b) Collados, J. F.; Ortiz, P.;
Harutyunyan, S. R. Eur. J. Org. Chem. 2016, 3065.
Chem. Rev. 2003, 103, 1449. (c) Namyslo, J. C.; Kaufmann, D. E. Chem.
Rev. 2003, 103, 1485. (d) Roy, S. R.; Eijsberg, H.; Bruffaerts, J.; Marek,
I. Chem. Sci. 2017, 8, 334. (e) Maturi, M. M.;Bach, T. Angew. Chem.
Int. Ed. 2014, 53, 7661. (f) Lopez-Carrillo, V.; Echavarren, A. M. J. Am.
Chem. Soc. 2010, 132, 9292. (g) Nishimura, A.; Ohashi, M.; Ogoshi, S.
J. Am. Chem. Soc. 2012, 134, 15692. (h) Liu, Y.; Liu, M. and Song, Z. J.
Am. Chem. Soc. 2005, 127, 3662. (i) Frebault, F.; Luparia, M.; Oliveira,
M. T.; Goddard, R.; Maulide, N. Angew. Chem., Int. Ed. 2010, 49,
5672.(j) Barluenga, J.; Riesgo, L.; Lopez, L. A.; Rubio, E. and Tom. M.
Angew. Chem. Int. Ed. 2009, 48, 7569. (k) Shi, M.; Liu, L.-P. and
Tang, J. J. Am. Chem. Soc. 2006, 128, 7430. (l) Xu, H.; Zhang, W.; Shu,
D.; Werness, J. B. and Tang, W. Angew. Chem. Int. Ed. 2008, 47, 8933.
16. Masarwa, A.; Fürstner, A.; Marek, I. Chem. Commun. 2009,
5760.
1
2
3
4
5
6
7
8
7. For examples with retention of configuration, see: (a) Hudrlik, P.
F.; Hudrlik, A. M.; Kulkarni, A. K. J. Am. Chem. Soc. 1982, 104, 6809.
(b) Simov, B. P.; Wuggenig, F.; Mereiter, K.; Andres, H.; France, J.;
Schnelli, P.; Hammerschmidt, F. J. Am. Chem. Soc. 2005, 127, 13934.
(c) Unger, R.; Weisser, F.; Chinkov, N.; Stanger, A.; Cohen, T.; Marek,
I. Org. Lett. 2009, 11, 1853.
8. For examples with inversion of configuration, see: (a) Biern-
baum, M. S.; Mosher, H. S. J. Am. Chem. Soc. 1971, 93, 6221. (b) Brook,
A. G.; Pascoe, J. D. J. Am. Chem. Soc. 1971, 93, 6224.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
9. Zhang, F.-G.; Eppe, G.; Marek, I. Angew. Chem. Int. Ed. 2016, 55,
714.
10. For selected examples of carbene formation from acylsilane,
see: (a) Becker, P.; Pirwerdjan, R.; Bolm, C. Angew. Chem. Int. Ed.
2015, 54, 15493. (b) Becker, P.; Priebbenow, D. L.; Pirwerdjan, R.;
Bolm, C. Angew. Chem. Int. Ed. 2014, 53, 269. (c) Shen, Z.; Dong, V.
M. Angew. Chem. Int. Ed. 2009, 48, 784. (d) Lu, P.; Feng, C.; Loh, T.-P.
Org. Lett. 2015, 17, 3210. (e) Baines, K. M. Chem. Commun. 2013, 49,
6366. (f) Brook, A. G.; Kucera, H. W.; Pearce, R. Can. J. Chem.1971, 49,
1618.
11. (a) Brook, A. G.; Dillon, P. G. Can. J. Chem.1969, 47, 4347. (b)
Atwell, W. H.; Weyenberg, D. R.; Uhlmann, J. G. J. Am. Chem. Soc.
1969, 91, 2025.
12. (a) Buswell, M.; Fleming, I.; Ghosh, U.; Mack, S.; Russell, M.;
Clark, B. P. Org. Biomol. Chem. 2004, 2, 3006. (b) Fleming, I.; Mack,
S.; Clark, B. P. Chem. Commun. 1998, 713.
17. For recent examples, see: (a) Xu, H.; Zhang, W.; Shu, D.; Wer-
ness, J. B. and Tang, W. Angew. Chem. Int. Ed. 2008, 47, 8933. (b)
Kleinbeck, F. and Toste, F. D. J. Am. Chem. Soc. 2009, 131, 9178. (c)
Barluenga, J.; Riesgo, L.; López, L. A.; Rubio, E. and Tomás, M. Angew.
Chem. Int. Ed. 2009, 48, 7569. (d) Li, C.-W.; Pati, K.; Lin, G.-Y.; Sohel,
S. M. A.; Hung, H.-H. and Liu, R.-S. Angew. Chem. Int. Ed. 2010, 49,
9891.
18. (a) Eppe, G.; Didier, D.; Marek, I. Chem. Rev. 2015, 115, 9175. (b)
Müller, D.; Marek, I. Chem. Soc. Rev. 2016, 45, 4552. (c) Marek, I.;
Simaan, S.; Masarwa, A. Angew. Chem. Int. Ed. 2007, 46, 7364. (d)
Didier, D.; Delaye, P.-O.; Simaan, M.; Island, B.; Eppe, G.; Eijsberg,
H.; Kleiner, A.; Knochel, P.; Marek, I. Chem. Eur. J. 2014, 20, 1038. (e)
Müller, D.; Marek, I. J. Am. Chem. Soc. 2015, 137, 15414.
19. If the migration proceeds with a lost of the configuration, a
mixture of diastereoisomer would be expected.
20. Roy, S. R.; Didier, D.; Kleiner, A.; Marek, I. Chem. Sci. 2016, 7,
5989.
21. Preshel-Zlatsin, M.; Zhang, F.-G.; Eppe, G.; Marek, I. Synthesis,
2016, 48, 3279.
22. Whereas n-BuLi led to only the Brook product after hydrolysis
(see the supporting information), Et2Zn has no effect and 2 is fully
recovered after hydrolysis. If the reaction is performed with a cata-
lytic amount of Grignard reagent, the same catalytic amount of cy-
clobutene is obtained.
23. CCDC 1481882 (2n), CCDC 1484247 (3E) and CCDC 1518467 (3N)
contain the supplementary crystallographic data for this paper. The-
se data can be obtained free of charge from The Cambridge Crystal-
lographic Data Centre.
13. For a recent review, see: Mack, D. J. and Njardarson, J. T. ACS
Catal. 2013, 3, 272. (b) Fürstner, A.; Aïssa, C. J. Am. Chem. Soc. 2006,
128, 6306. (c) Shi, M.; Liu, L.-P.; Tang, J. J. Am. Chem. Soc. 2006, 128,
7430.
14. For recent reviews, see: (a) Misale, A.; Niyomchon, S.; Maulide,
N. Acc. Chem. Res. 2016, 49, 2444. (b) Xu, Y.; Conner, M. L.; Brown,
M. K. Angew. Chem. Int. Ed. 2015, 54, 11918. (c) Dembitsky, V. M.
Phytomedicine 2014, 21, 1559. (d) Fan, Y.-Y.; Gao, X.-H.; Yue, J.-M. Sci.
China Chem. 2016, 59, 1126. (e) Beniddir, M. A.; Evanno, L.; Joseph,
D.; Skiredj, A.; Poupon, E. Nat. Prod. Rep. 2016, 33, 820. (f) Souris, C.;
Frébault, F.; Patel, A.; Audisio, D.; Houk, K. N.; Maulide, N. Org.
Lett. 2013, 15, 3242. (g) Souris, C.; Misale, A.; Chen, Y.; Luparia, M.;
Maulide, N. Org. Lett. 2015, 17, 4486. (h) Ito, H.; Hasegawa, M.;
Takenaka, Y.; Kobayashi, T.; Iguchi, K. J. Am. Chem. Soc. 2004, 126,
4520. (i) Kang, T.; Ge, S.; Lin, L.; Lu, Y.; Liu, X.; Feng, X. Angew.
Chem. Int. Ed. 2016, 55, 5541.
24. Lou, Y.; Remarchuk, T. P.; Corey, E. J. J. Am. Chem. Soc. 2005,
127, 14223.
15. For a few reviews, see: (a) Xu, Y.; Conner, M. L.; Brown, M. K.
Angew. Chem. Int. Ed. 2015, 54, 11918. (b) Lee-Ruff, E.; Mladenova, G.
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