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33845939523
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Sturino, C. F.; Lachance, N.; Berthelette, C.; Li, L.; Wang, Z. U.S. Patent 0124680, 2005.
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Sturino, C.F.1
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Berthelette, C.3
Li, L.4
Wang, Z.5
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15
-
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33845945109
-
-
Methods have been reported for setting the chiral center in 2
-
Methods have been reported for setting the chiral center in 2. See refs 16-18.
-
See refs
, pp. 16-18
-
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16
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11844265889
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Campos, K. R.; Journet, M.; Lee, S.; Grabowski, E. J. J.; Tillyer, R. D. J. Org. Chem. 2005, 70, 268-274.
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Lee, S.3
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Tillyer, R.D.5
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24944574402
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Shafiee, A.; Upadhyay, V.; Corley, E. G.; Biba, M.; Zhao, D.; Marcoux, J.-F.; Campos, K. R.; Journet, M.; King, A. O.; Larsen, R. D.; Grabowski, E. J. J.; Volante, R. P.; Tillyer, R. D. Tetrahedron: Asymmetry 2005, 16, 3094-3098.
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Shafiee, A.1
Upadhyay, V.2
Corley, E.G.3
Biba, M.4
Zhao, D.5
Marcoux, J.-F.6
Campos, K.R.7
Journet, M.8
King, A.O.9
Larsen, R.D.10
Grabowski, E.J.J.11
Volante, R.P.12
Tillyer, R.D.13
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26844479020
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McKeown, A.E.5
Tillyer, R.D.6
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19
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0025778593
-
-
For a diastereoselective heterogeneous hydrogenation of an indole α,β-unsaturated ester, see
-
For a diastereoselective heterogeneous hydrogenation of an indole α,β-unsaturated ester, see: Beard, R. L.; Meyers, A. I. J. Org. Chem. 1991, 56, 2091-2096.
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, pp. 2091-2096
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Beard, R.L.1
Meyers, A.I.2
-
20
-
-
13344287589
-
-
For a diastereoselective homogeneous exocyclic α,β-unsaturated ester, see
-
For a diastereoselective homogeneous exocyclic α,β-unsaturated ester, see: Ohba, M.; Haneishi, T.; Fujii, T. Heterocycles 1994, 38, 2253-2265.
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(1994)
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, vol.38
, pp. 2253-2265
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Ohba, M.1
Haneishi, T.2
Fujii, T.3
-
21
-
-
33845963321
-
-
For examples of asymmetric exocyclic dehydroamino acid hydrogenations, see refs 22-25
-
For examples of asymmetric exocyclic dehydroamino acid hydrogenations, see refs 22-25.
-
-
-
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22
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3843051570
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Jiang, X.; van den Berg, M.; Minnaard, A. J.; Feringa, B. L.; de Vries, J. G. Tetrahedron: Asymmetry 2004, 15, 2223-2229.
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, pp. 2223-2229
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Jiang, X.1
van den Berg, M.2
Minnaard, A.J.3
Feringa, B.L.4
de Vries, J.G.5
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3042716629
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Imamoto, T.; Oohara, N.; Takahashi, H. Synthesis 2004, 9, 1353-1358.
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, pp. 1353-1358
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Imamoto, T.1
Oohara, N.2
Takahashi, H.3
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24
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0042699953
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Oohara, N.; Katagiri, K.; Imamoto, T. Tetrahedron: Asymmetry 2003, 14, 2171-2175.
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Oohara, N.1
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Imamoto, T.3
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0036329765
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Ohashi, A.; Kikuchi, S.; Yasutake, M.; Imamoto, T. J. Org. Chem. 2002, 15, 2535-2546.
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Ohashi, A.1
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33845941391
-
-
Manuscript in preparation
-
Humphrey, G. R.; et al. Manuscript in preparation.
-
-
-
Humphrey, G.R.1
-
27
-
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33845953375
-
-
4 to give the corresponding chiral ester in 88% ee.
-
4 to give the corresponding chiral ester in 88% ee.
-
-
-
-
29
-
-
0000578244
-
-
Ohta, T.; Takaya, H.; Kitaniura, M.; Nagai, K.; Noyori, R. J. Org. Chem. 1987, 52, 3176-3178.
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-
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Ohta, T.1
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Kitaniura, M.3
Nagai, K.4
Noyori, R.5
-
30
-
-
33845963597
-
-
Compound 1 exhibited poor solubility in most solvents at room temperature. A detailed list of solubilities can be found in the Supporting Information.
-
Compound 1 exhibited poor solubility in most solvents at room temperature. A detailed list of solubilities can be found in the Supporting Information.
-
-
-
-
31
-
-
33845923858
-
-
Synthesis of 1-Br-E employing the chemistry used to prepare 1-E results in 10-30% debromination.
-
Synthesis of 1-Br-E employing the chemistry used to prepare 1-E results in 10-30% debromination.
-
-
-
-
32
-
-
0000676432
-
-
Mashima, K.; Kusano, K.; Sato, N.; Matsumura, Y.; Nozaki, K.; Kumobayashi, H.; Sayo, N.; Hori, Y.; Ishizaki, T.; Akutagawa, S.; Takaya, H. J. Org. Chem. 1994, 59, 3064-3076.
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-
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Mashima, K.1
Kusano, K.2
Sato, N.3
Matsumura, Y.4
Nozaki, K.5
Kumobayashi, H.6
Sayo, N.7
Hori, Y.8
Ishizaki, T.9
Akutagawa, S.10
Takaya, H.11
-
33
-
-
33845930797
-
-
For reviews on the application of BINAP and its derivatives to asymmetric catalysis, see refs 34-36.
-
For reviews on the application of BINAP and its derivatives to asymmetric catalysis, see refs 34-36.
-
-
-
-
35
-
-
0034974831
-
-
Kumobayashi, H.; Miura, T.; Sayo, N.; Saito, T.; Zhang, X. Synlett 2001, 1055.
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(2001)
Synlett
, pp. 1055
-
-
Kumobayashi, H.1
Miura, T.2
Sayo, N.3
Saito, T.4
Zhang, X.5
-
37
-
-
33845923856
-
-
This is supported by the NMR spectroscopic observation that thermolysis of 3 in the presence of stoichiometric 1-E liberates p-cymene over ca. 6 min
-
This is supported by the NMR spectroscopic observation that thermolysis of 3 in the presence of stoichiometric 1-E liberates p-cymene over ca. 6 min.
-
-
-
-
38
-
-
33845947911
-
-
Assay yields were determined by preparing a known concentration of analytically pure 2 and comparing the UV response (HPLC) of this solution against that of a hydrogenation reaction solution.
-
Assay yields were determined by preparing a known concentration of analytically pure 2 and comparing the UV response (HPLC) of this solution against that of a hydrogenation reaction solution.
-
-
-
-
39
-
-
33845933347
-
-
In all cases, percent conversions refer to HPLC area percent measured at 215 nm. Conversion, area product, area product, area starting material
-
In all cases, percent conversions refer to HPLC area percent measured at 215 nm. Conversion = (area product)/(area product + area starting material).
-
-
-
-
40
-
-
33845932541
-
-
Heating a methanol solution of 1-E·TMG in the absence of catalyst for 12 h at 50 °C does not produce 1-Endo·TMG.
-
Heating a methanol solution of 1-E·TMG in the absence of catalyst for 12 h at 50 °C does not produce 1-Endo·TMG.
-
-
-
-
42
-
-
33845928441
-
-
Photolysis of 1-E·TMG in CD3OD does not incorporate deuterium into either 1-E·TMG or 1-Z·TMG.
-
Photolysis of 1-E·TMG in CD3OD does not incorporate deuterium into either 1-E·TMG or 1-Z·TMG.
-
-
-
-
45
-
-
0026634140
-
-
Yoshikawa, K.; Murata, M.; Yamamoto, N.; Inoguchi, K.; Achiawa, K. Chem. Pharm. Bull. 1992, 40, 1072-1074.
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, pp. 1072-1074
-
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Yoshikawa, K.1
Murata, M.2
Yamamoto, N.3
Inoguchi, K.4
Achiawa, K.5
-
46
-
-
0000529157
-
-
Saburi, M.; Takeuchi, H.; Ogasawara, M.; Tsukahara, T.; Ishii, Y.; Ikariya, T.; Takahashi, T.; Uchida, Y. J. Organomet. Chem. 1992, 428, 155-167.
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Saburi, M.1
Takeuchi, H.2
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Tsukahara, T.4
Ishii, Y.5
Ikariya, T.6
Takahashi, T.7
Uchida, Y.8
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47
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0032463143
-
-
Daley, C. J. A.; Wiles, J. A.; Bergens, S. H. Can. J. Chem. 1998, 76, 1447-1456.
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Can. J. Chem
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, pp. 1447-1456
-
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Daley, C.J.A.1
Wiles, J.A.2
Bergens, S.H.3
-
48
-
-
33845953065
-
-
Solutions of pure 1-Endo in the presence of catalyst isomerize to generate an equilibrium mixture with 1-E. As such, we opted to start with the equilibrated mixture instead of pure 1-Endo to ensure that the starting concentration of 1-Endo was constant between experiments. Consistent with results from Figure 7, the high-pressure syringe pump addition of catalyst to a solution of 1-Endo at 100 psig H2 and 50 °C produced 2 in 92% ee.
-
Solutions of pure 1-Endo in the presence of catalyst isomerize to generate an equilibrium mixture with 1-E. As such, we opted to start with the equilibrated mixture instead of pure 1-Endo to ensure that the starting concentration of 1-Endo was constant between experiments. Consistent with results from Figure 7, the high-pressure syringe pump addition of catalyst to a solution of 1-Endo at 100 psig H2 and 50 °C produced 2 in 92% ee.
-
-
-
-
49
-
-
33845925753
-
-
At 515 psi, the reaction rate was sufficiently fast that complete consumption of 1-Endo isomer and some of the 1-E isomer had occurred at 20 area, conversion. The point at 10 area, conversion at 515 psi is calculated by removing the contribution from 1-E
-
At 515 psi, the reaction rate was sufficiently fast that complete consumption of 1-Endo isomer and some of the 1-E isomer had occurred at 20 area % conversion. The point at 10 area % conversion at 515 psi is calculated by removing the contribution from 1-E.
-
-
-
-
50
-
-
33845929977
-
-
This information can be found in the Supporting Information
-
This information can be found in the Supporting Information.
-
-
-
-
51
-
-
33845924367
-
-
An identical result is obtained when the relative ratios of the R and S enantiomers are used in place of %ee
-
An identical result is obtained when the relative ratios of the R and S enantiomers are used in place of %ee.
-
-
-
-
52
-
-
33845942693
-
-
Qualitatively, the Z isomer was less reactive than the E isomer toward hydrogenation with 3.
-
Qualitatively, the Z isomer was less reactive than the E isomer toward hydrogenation with 3.
-
-
-
-
53
-
-
0035600833
-
-
Bulliard, M.; Laboue, B.; Lastennet, J.; Roussiasse Org. Process Res. Dev. 2001, 5, 438-441.
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Boulton, L.T.1
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0007361075
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Yamamoto, K.; Ikeda, K.; Yin, L. K. J. Organomet. Chem. 1989, 370, 319-332.
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Yamamoto, K.1
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0038722894
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Ager, D. J.; Babler, S.; Froen, D. E.; Laneman, S. A.; Pantaleone, D. P.; Prakash, I.; Zhi, B. Org. Process Res. Dev. 2003, 7, 369-378.
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Ager, D.J.1
Babler, S.2
Froen, D.E.3
Laneman, S.A.4
Pantaleone, D.P.5
Prakash, I.6
Zhi, B.7
-
60
-
-
33845960459
-
-
2, was employed because catalyst 3 does not react with the free acid. It is thought that base is required to facilitate cymene displacement and generation of the active catalyst.
-
2, was employed because catalyst 3 does not react with the free acid. It is thought that base is required to facilitate cymene displacement and generation of the active catalyst.
-
-
-
-
61
-
-
33845930529
-
-
2 with and without TMG was 92-93.%.
-
2 with and without TMG was 92-93.%.
-
-
-
-
62
-
-
33646704228
-
-
Daley, C. J. A.; Wiles, J. A.; Bergens, S. H. Inorg. Chim. Acta 2006, 359, 2760-2770.
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(2006)
Inorg. Chim. Acta
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, pp. 2760-2770
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Daley, C.J.A.1
Wiles, J.A.2
Bergens, S.H.3
-
63
-
-
33845934425
-
-
A similar observation was noted by Chan and co-workers in the hydrogenation of a naproxen precursor with a ruthenium catalyst under basic conditions. See ref 64
-
A similar observation was noted by Chan and co-workers in the hydrogenation of a naproxen precursor with a ruthenium catalyst under basic conditions. See ref 64.
-
-
-
-
64
-
-
0003022354
-
-
Chan, A. S. C.; Chen, C. C.; Yang, T. K.; Huang, J. H.; Lin, Y. C. Inorg. Chim. Acta 1995, 234, 95-100.
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(1995)
Inorg. Chim. Acta
, vol.234
, pp. 95-100
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Chan, A.S.C.1
Chen, C.C.2
Yang, T.K.3
Huang, J.H.4
Lin, Y.C.5
-
65
-
-
33845964114
-
-
The substrate is assumed to be bound to the metal via the carboxylate linkage. This is supported by literature reports (see ref 57 and 66) and the observation that the methyl ester derivative of 1 is not hydrogenated by 3
-
The substrate is assumed to be bound to the metal via the carboxylate linkage. This is supported by literature reports (see ref 57 and 66) and the observation that the methyl ester derivative of 1 is not hydrogenated by 3.
-
-
-
-
66
-
-
0000891934
-
-
Ashby, M. T.; Khan, M. A.; Halpern, J. Organometallics 1991, 10, 2011-2015.
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(1991)
Organometallics
, vol.10
, pp. 2011-2015
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Ashby, M.T.1
Khan, M.A.2
Halpern, J.3
-
67
-
-
33845961481
-
-
A reviewer is acknowledged tor suggesting this two-point binding mechanism to rationalize the higher enantioselectivity
-
A reviewer is acknowledged tor suggesting this two-point binding mechanism to rationalize the higher enantioselectivity.
-
-
-
-
68
-
-
33751391785
-
-
Kitamura, M.; Tokunaga, M.; Noyori, R. J. Org. Chem. 1992, 57, 4053-4054.
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Kitamura, M.1
Tokunaga, M.2
Noyori, R.3
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69
-
-
33845952583
-
-
In the absence of hydrogen, methanolic solutions of 1-E·TMG and 3 were found to liberate small quantities of the catalyst poisons dimethylamine and ammonia over 24 h GC analysis, In order to maximize catalyst turnover, solutions of the catalyst 3 were added immediately prior to hydrogen addition
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In the absence of hydrogen, methanolic solutions of 1-E·TMG and 3 were found to liberate small quantities of the catalyst poisons dimethylamine and ammonia over 24 h (GC analysis). In order to maximize catalyst turnover, solutions of the catalyst 3 were added immediately prior to hydrogen addition.
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