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1
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28244463546
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Kubanek, J.; Prusak, A. C.; Snell, T. W.; Giese, R. A.; Hardcastle, K. I.; Fairchild, C. R.; Aalbersberg, W.; Raventos-Suarez, C.; Hay, M. E. Org. Lett. 2005, 7, 5261-5264
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2
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33745778863
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3
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64249149265
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Lane, A. L.; Stout, E. P.; Lin, A.-.S.; Prudhomme, J.; Le Roch, K.; Fairchild, C. R.; Franzblau, S. G.; Hay, M. E.; Aalbersberg, W.; Kubanek, J. J. Org. Chem. 2009, 74, 2736-2742
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4
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77749243103
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Lin, A. S.; Stout, E. P.; Prudhomme, J.; Le Roch, K.; Fairchild, C. R.; Franzblau, S. G.; Aalbersberg, W.; Hay, M. E.; Kubanek, J. J. Nat. Prod. 2010, 73, 275-278
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5
-
-
77950341605
-
-
Though alkenes 1, 2, and 3 are likely to form cyclic bromonium ions at similar rates, bromonium transfer between alkenes is likely to be rapidly reversible, so that the reaction outcome is determined by the relative rates at which these various species react further:;;,-1233
-
Though alkenes 1, 2, and 3 are likely to form cyclic bromonium ions at similar rates, bromonium transfer between alkenes is likely to be rapidly reversible, so that the reaction outcome is determined by the relative rates at which these various species react further: Denmark, S. E.; Burk, M. T.; Hoover, A. J. J. Am. Chem. Soc. 2010, 132, 1232-1233
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Denmark, S.E.1
Burk, M.T.2
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8
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0031335733
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Neverov, A. A.; Muise, T. L.; Brown, R. S. Can. J. Chem. 1997, 75, 1844-1850
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Neverov, A.A.1
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Brown, R.S.3
-
11
-
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0028789811
-
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Ligand 9: A related ligand:; Org. Lett. 2001, 3, 3211-3214
-
Ligand 9: Corey, E. J.; Noe, M. C.; Lin, S. Tetrahedron Lett. 1995, 36, 8741-8744 A related ligand: Corey, E. J.; Zhang, J. Org. Lett. 2001, 3, 3211-3214
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-
12
-
-
79952147945
-
-
Determined by Mosher ester analysis (see Supporting Information).
-
Determined by Mosher ester analysis (see Supporting Information).
-
-
-
-
13
-
-
34247246165
-
-
Morimoto, Y.; Okita, T.; Takaishi, M.; Tanaka, T. Angew. Chem., Int. Ed. 2007, 46, 1132-1135
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Morimoto, Y.1
Okita, T.2
Takaishi, M.3
Tanaka, T.4
-
15
-
-
79952177394
-
-
The bromohydrin derived from ester 11 could not be converted to acid 13, due to multiple side reactions under a variety of basic and Lewis acidic ester cleavage conditions.
-
The bromohydrin derived from ester 11 could not be converted to acid 13, due to multiple side reactions under a variety of basic and Lewis acidic ester cleavage conditions.
-
-
-
-
16
-
-
38449088641
-
-
Shiina, I.; Fukui, H.; Sasaki, A. Nat. Protoc. 2007, 2, 2312-2317
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Shiina, I.1
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17
-
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1642334165
-
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Shiina, I.; Kubota, M.; Oshiumi, H.; Hashizume, M. J. Org. Chem. 2004, 69, 1822-1830
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Shiina, I.1
Kubota, M.2
Oshiumi, H.3
Hashizume, M.4
-
18
-
-
79952169871
-
-
Slow addition of substrate (48 h) and elevated temperature (50 °C) were critical in order to ensure that the seco acid was consumed faster than it was added, preventing diolide formation. These conditions were robust on a scale of several hundered milligrams.
-
Slow addition of substrate (48 h) and elevated temperature (50 °C) were critical in order to ensure that the seco acid was consumed faster than it was added, preventing diolide formation. These conditions were robust on a scale of several hundered milligrams.
-
-
-
-
19
-
-
79952135371
-
-
See Supporting Information.
-
See Supporting Information.
-
-
-
-
20
-
-
79952149886
-
-
Other reagents employed included NBS, NBS/acids, NBS/phosphines, and TBCHD (2,4,4,6-tetrabromocyclohexadienone).
-
Other reagents employed included NBS, NBS/acids, NBS/phosphines, and TBCHD (2,4,4,6-tetrabromocyclohexadienone).
-
-
-
-
21
-
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77957719306
-
-
Snyder, S. A.; Treitler, D. S.; Brucks, A. P. J. Am. Chem. Soc. 2010, 132, 14303-14314
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23
-
-
79952127995
-
-
We presume this highly polar solvent mixture to be helpful in prolonging the life of the cationic intermediate 19 long enough for the slow cyclization step to occur. Potentially, this solvent may also promote a compact and more cyclization-prone conformation of 19 via hydrophobic effects.
-
We presume this highly polar solvent mixture to be helpful in prolonging the life of the cationic intermediate 19 long enough for the slow cyclization step to occur. Potentially, this solvent may also promote a compact and more cyclization-prone conformation of 19 via hydrophobic effects.
-
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-
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24
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84982207554
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a of the conjugate acid of dimethylsulfide is -5 (see:,-403), making it far less basic than leaving groups derived from other bromonium sources. A reviewer has suggested that BDSB may generally give cleaner reactions because its high reactivity allows the use of lower temperatures
-
a of the conjugate acid of dimethylsulfide is -5 (see: Arnett, E. M. Prog. Phys. Org. Chem. 1963, 1, 223-403), making it far less basic than leaving groups derived from other bromonium sources. A reviewer has suggested that BDSB may generally give cleaner reactions because its high reactivity allows the use of lower temperatures
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Selected examples
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42
-
-
79952160200
-
-
See Supporting Information for a full discussion of NMR data.
-
See Supporting Information for a full discussion of NMR data.
-
-
-
-
43
-
-
79952128314
-
-
note
-
To claim selectivity, we must claim the absence of significant regio-and diastereomers of 7 and 15. LC of the crude product mixture shows no significant quantities of additional cyclization products. The identified products comprise >80% of the crude LC; the only unidentified product present at greater than 3% abundance is quickly solvolyzed in methanol and is presumably a diastereo-or regioisomer of allylic bromide 16.
-
-
-
-
44
-
-
79952164104
-
-
note
-
11-bis-epi -Bromophycolide S.
-
-
-
|