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For other examples of α-chlorination reactions see: c
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18044378817
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For a recent review see; h
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Oestreich, M.1
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1842555125
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S. France, H. Wack, A. E. Taggi, A. M. Hafez, T. R. Wagerle, M. H. Shah, C. L. Dusich, T. Lectka, J. Am. Chem. Soc. 2004, 126, 4245-4255.
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France, S.1
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Shah, M.H.6
Dusich, C.L.7
Lectka, T.8
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10
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0028597438
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Halomon: a R. W. Fuller, J. H. Cardellina II, J. Jurek, P. J. Scheuer, B. Alvarado-Lindner, M. McGuire, G. N. Gray, J. R. Steiner, J. Clardy, E. Menez, R. H. Shoemaker, D. J. Newman, K. M. Snader, M. R. Boyd, J. Med Chem. 1994, 37, 4407-4411.
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Halomon: a) R. W. Fuller, J. H. Cardellina II, J. Jurek, P. J. Scheuer, B. Alvarado-Lindner, M. McGuire, G. N. Gray, J. R. Steiner, J. Clardy, E. Menez, R. H. Shoemaker, D. J. Newman, K. M. Snader, M. R. Boyd, J. Med Chem. 1994, 37, 4407-4411.
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28244463546
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Bromophycolide A: b J. Kubanek, A. C. Prusak, T. W. Snell, R. A. Giese, K. I. Hardcastle, C. R. Fairchild, W. Aalbersberg, C. Raventos-Suarez, M. E. Hay, Org. Lett. 2005, 7, 5261-5264.
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Bromophycolide A: b) J. Kubanek, A. C. Prusak, T. W. Snell, R. A. Giese, K. I. Hardcastle, C. R. Fairchild, W. Aalbersberg, C. Raventos-Suarez, M. E. Hay, Org. Lett. 2005, 7, 5261-5264.
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A. M. Hafez, A. E. Taggi, H. Wack, J. Esterbrook, T. Lectka, Org. Lett. 2001, 3, 2049-2051.
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Hafez, A.M.1
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15
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34250657355
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in press
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C. Dogo-Isonagie, T. Bekele, S. France, J. Wolfer, A. Weatherwax, A. E. Taggi, T. Lectka, J. Org. Chem. in press.
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J. Org. Chem
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Dogo-Isonagie, C.1
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France, S.3
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Lectka, T.7
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0037067063
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A. E. Taggi, A. M. Hafez, H. Wack, B. Young, D. Ferraris, T. Lectka, J. Am. Chem. Soc. 2002, 124, 6626-6636.
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0037037845
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Taggi, A.E.1
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Dudding, T.3
Lectka, T.4
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18
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34250661416
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See Supporting Information for details
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See Supporting Information for details.
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19
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0141772172
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L. A. Paquette, G. J. Hefferon, R. Samodral, Y. Hanzawa, J. Org. Chem. 1983, 48, 1262-1266.
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Paquette, L.A.1
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Hanzawa, Y.4
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20
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34250641494
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Molecular mechanics calculations confirm that there is a less than 0.5 kcal/mol difference between the diastereomeric acylammonium intermediates
-
Molecular mechanics calculations confirm that there is a less than 0.5 kcal/mol difference between the diastereomeric acylammonium intermediates.
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21
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0000019953
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R. R. Soelch, G. W. Mauer, D. M. Lemal, J. Org. Chem. 1985, 50, 5845-5852.
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Soelch, R.R.1
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23
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0037037845
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A. E. Taggi, A. M. Hafez, T. Dudding, T. Lectka, Tetrahedron 2002, 58, 8351-8356.
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Tetrahedron
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Taggi, A.E.1
Hafez, A.M.2
Dudding, T.3
Lectka, T.4
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24
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34250656127
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A combination of IMOMO (integrated molecular orbital + MO method) variation of ONIOM (n-layered integrated molecular orbital method) at the HF3-21G(d)//AM1 level, coupled with constrained Monte-Carlo conformational searches (MCMM) to generate initial IMOMO geometries.
-
A combination of IMOMO (integrated molecular orbital + MO method) variation of ONIOM (n-layered integrated molecular orbital method) at the HF3-21G(d)//AM1 level, coupled with constrained Monte-Carlo conformational searches (MCMM) to generate initial IMOMO geometries.
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25
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34250679331
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M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr, T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B
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M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian 03, revision B. 04, Gaussian, Inc., Pittsburgh, PA, 2003.
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27
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34250689099
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The enolate carbon-bromine distances are 2.07 Å in TS1 and 2.09 Å in TS2. The quinone carbon-bromine distances are 2.69 Å in TS1 and 2.74 Å in TS2.
-
The enolate carbon-bromine distances are 2.07 Å in TS1 and 2.09 Å in TS2. The quinone carbon-bromine distances are 2.69 Å in TS1 and 2.74 Å in TS2.
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28
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34250622001
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These bonds have measured distances of 2.26 Å, 2.41 Å, and 2.51 Å in TS1; and 2.28 Å, 2.29 Å, and 2.51 Å in TS2.
-
These bonds have measured distances of 2.26 Å, 2.41 Å, and 2.51 Å in TS1; and 2.28 Å, 2.29 Å, and 2.51 Å in TS2.
-
-
-
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29
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34250685760
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f = +0.21 in TS2.
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f = +0.21 in TS2.
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-
-
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30
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34250683748
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The ketene enolate oxygen-quinuclidine hydrogen distances are 2.37 Å and 2.51 Å in TS1 and, 2.36 Å and 2.51 Å in TS2.
-
The ketene enolate oxygen-quinuclidine hydrogen distances are 2.37 Å and 2.51 Å in TS1 and, 2.36 Å and 2.51 Å in TS2.
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-
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31
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34250663511
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Final energies represent ΔE values computed using the IMOMO method at the HF3-21G(d)//AM1 level. Reported Mulliken charges were determined at the B3LYP/6-31(d) level of theory through single-point calculations using optimized IMOMO geometries. Select hydrogens have been removed for simplicity.
-
Final energies represent ΔE values computed using the IMOMO method at the HF3-21G(d)//AM1 level. Reported Mulliken charges were determined at the B3LYP/6-31(d) level of theory through single-point calculations using optimized IMOMO geometries. Select hydrogens have been removed for simplicity.
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32
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34250660104
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Among these are elongated quinone⋯Br bond lengths of 2.59 Å and 2.60 Å, and short enolate⋯Br distances of 2.17 Å and 2.18 Å, which are consistent with halogen transfer occurring late on the reaction coordinate.
-
Among these are elongated quinone⋯Br bond lengths of 2.59 Å and 2.60 Å, and short enolate⋯Br distances of 2.17 Å and 2.18 Å, which are consistent with halogen transfer occurring late on the reaction coordinate.
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33
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0037134937
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+-C-H⋯O=C hydrogen bond interactions, see: C. E. Cannizzaro, K. N. Houk, J. Am. Chem. Soc. 2002, 124, 7163-7169.
-
+-C-H⋯O=C hydrogen bond interactions, see: C. E. Cannizzaro, K. N. Houk, J. Am. Chem. Soc. 2002, 124, 7163-7169.
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-
-
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34
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34250646597
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Stochastic molecular dynamics simulations performed using the MMFFs force field as implemented in Macromodel 7.1. The plotted trajectories represent the average values obtained from 5 independent simulations conducted at 195.15 K and 1 atm in vacuo. Initial equilibration and minimizations were not performed due to the instability associated with transition state geometries being potential energy maxima on the reaction surface
-
Stochastic molecular dynamics simulations performed using the MMFFs force field as implemented in Macromodel 7.1. The plotted trajectories represent the average values obtained from 5 independent simulations conducted at 195.15 K and 1 atm in vacuo. Initial equilibration and minimizations were not performed due to the instability associated with transition state geometries being potential energy maxima on the reaction surface.
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35
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33746922226
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For a discussion on reaction trajectories for addition to carbonyls, see
-
For a discussion on reaction trajectories for addition to carbonyls, see: H. B. Buergi, J. D. Dunitz, Ace. Chem. Res. 1983, 16, 153-161.
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Ace. Chem. Res
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Buergi, H.B.1
Dunitz, J.D.2
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36
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0141580891
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a) H. C. Brown, M. D. Taylor, M. Gerstein, H. Bartholomay, J. Am. Chem. Soc. 1944, 66, 431-435;
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Brown, H.C.1
Taylor, M.D.2
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37
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20644444926
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b) H. C. Brown, Science 1946, 103, 385;
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Science
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Brown, H.C.1
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39
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4143093678
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Recent reviews of asymmetric epoxidation: a
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Recent reviews of asymmetric epoxidation: a) C. L. Winn, V. K. Aggarwal, Acc. Chem. Res. 2004, 37, 611-620;
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Winn, C.L.1
Aggarwal, V.K.2
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1042265088
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L. P. C. Nielsen, C. P. Stevenson, D. G. Blackmond, E. N. Jacobsen, J. Am. Chem. Soc. 2004, 126, 1360-1362.
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Nielsen, L.P.C.1
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Jacobsen, E.N.4
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43
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34250638623
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[1e].
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[1e].
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44
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34250617062
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S. Takano, T Sugihara, T. Kamikubo, K. Ogasawara, Heterocycles 1991, 32, 1587-1591.
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Takano, S.1
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45
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37049073328
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Epoxide ee based on optical rotation. E. W. Collington, H. Finch, J. G. Montana, R. J. K. Taylor, J. Chem. Soc., Perkin Trans. 1 1990, 7, 1839-1843.
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Epoxide ee based on optical rotation. E. W. Collington, H. Finch, J. G. Montana, R. J. K. Taylor, J. Chem. Soc., Perkin Trans. 1 1990, 7, 1839-1843.
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