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The asymmetric Rh-catalyzed 1-allylindole C(2)-H bond activation has recently been applied successfully to the synthesis of a JTT-010 analogue. (a) For Rh-catalyzed C(2)-H bond activation of 1-allylindoles, see: Thalji, R. K.; Ellman, J. A.; Bergman, R. G. J. Am. Chem. Soc. 2004, 126, 7192-7193.
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The asymmetric Rh-catalyzed 1-allylindole C(2)-H bond activation has recently been applied successfully to the synthesis of a JTT-010 analogue. (a) For Rh-catalyzed C(2)-H bond activation of 1-allylindoles, see: Thalji, R. K.; Ellman, J. A.; Bergman, R. G. J. Am. Chem. Soc. 2004, 126, 7192-7193.
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(b) Wilson, R. M.; Thalji, R. K.; Bergman, R. G.; Ellman, J. A. Org. Lett. 2006, 8, 1745-1747.
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26
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15444359037
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Compound 2b was prepared from (R)-epichlorohydrin and diethyl malonate via one step. See: Sekiyama, T.; Hatsuya, S.; Tanaka, Y.; Uchiyama, M.; Ono, N.; Iwayama, S.; Oikawa, M.; Suzuki, K.; Okunishi, M.; Tsuji, T. J. Med. Chem. 1998, 41, 1284-1298.
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Compound 2b was prepared from (R)-epichlorohydrin and diethyl malonate via one step. See: Sekiyama, T.; Hatsuya, S.; Tanaka, Y.; Uchiyama, M.; Ono, N.; Iwayama, S.; Oikawa, M.; Suzuki, K.; Okunishi, M.; Tsuji, T. J. Med. Chem. 1998, 41, 1284-1298.
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27
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34548176267
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See Supporting Information for X-ray crystallographic data of 7. Oxidation of 7 followed by methyl esterification gave 9, defining the absolute configuration of 7 as depicted because 9 was also obtained from 8a, whose absolute configuration was authenticated by its conversion to JTT-010.
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See Supporting Information for X-ray crystallographic data of 7. Oxidation of 7 followed by methyl esterification gave 9, defining the absolute configuration of 7 as depicted because 9 was also obtained from 8a, whose absolute configuration was authenticated by its conversion to JTT-010.
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28
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0031660905
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Also see references cited therein
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(a) Moody, C. J.; Norton, C. L.; Slawin, A. M. Z.; Taylor, S. Anti-Cancer Drug Des. 1998, 13, 611-634. Also see references cited therein.
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34548173446
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Another reaction pathway involving nucleophilic attack at the methylene of 2b followed by decarboxylation and cyclization was ruled out since this pathway should not provide 7 but the enantiomer of 7
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Another reaction pathway involving nucleophilic attack at the methylene of 2b followed by decarboxylation and cyclization was ruled out since this pathway should not provide 7 but the enantiomer of 7.
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32
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34548148202
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Compound If was prepared in one step from 2-oxindole. See the Supporting Information.
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Compound If was prepared in one step from 2-oxindole. See the Supporting Information.
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33
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34548168565
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Unpurified 2b was used in this 100 g scale reaction batch
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Unpurified 2b was used in this 100 g scale reaction batch.
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34
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0000854668
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34548167773
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In this case, iterative operation was required to complete the reaction because partial lactone regeneration was competitive with the decarboxylation under acidic conditions
-
(c) In this case, iterative operation was required to complete the reaction because partial lactone regeneration was competitive with the decarboxylation under acidic conditions.
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37
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0034731631
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One of the minor isomers isolated from products of a chiral nitrone cycloaddition reaction was reportedly transformed into 10 ∼1% overall yield, Beccalli, E. M, Broggini, G, Rosa, C. L, Passarella, D, Pilati, T, Terraneo, A, Zecchi, G. J. Org. Chem. 2000, 65, 8924-8932
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One of the minor isomers isolated from products of a chiral nitrone cycloaddition reaction was reportedly transformed into 10 (∼1% overall yield). Beccalli, E. M.; Broggini, G.; Rosa, C. L.; Passarella, D.; Pilati, T.; Terraneo, A.; Zecchi, G. J. Org. Chem. 2000, 65, 8924-8932.
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