Journal of the American Chemical Society
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(2) For enantioselective, reverse prenylation of oxindoles, see: (a)
reverse prenylated indole in 80% yield. (b) In preliminary studies,
Trost, B. M.; Malhotra, S.; Chan, W. H. J. Am. Chem. Soc. 2011, 133,
7328. For enantioselective, reverse prenylation of isatins, see: (b)
Itoh, J.; Han, S. B.; Krische, M. J. Angew. Chem., Int. Ed. 2009, 48,
6313. For selected examples of one-step C3 reverse prenylation of C3
unsubstituted indoles, see: (c) Kimura, M.; Futamata, M.; Mukai, R.;
Tamaru, Y. J. Am. Chem. Soc. 2005, 127, 4592. (d) Usui, L.; Schmidt,
S.; Keller, M.; Breit, B. Org. Lett. 2008, 10, 1207. (e) Gruber, S.;
Zaitsev, A. B.; Woerle, M.; Pregosin, P. S.; Veiros, L. F.
Organometallics 2008, 27, 3796. (f) Sundararaju, B.; Achard, M.;
Demerseman, B.; Toupet, L.; Sharma, G. V. M.; Bruneau, C. Angew.
Chem., Int. Ed. 2010, 49, 2782.
(3) For selected enantioselective allylations, see: (a) Trost, B. M.;
Quancard, J. J. Am. Chem. Soc. 2006, 128, 6314. (b) Liu, Y.; Du, H.
Org. Lett. 2013, 15, 740. (c) Zhang, X.; Han, L.; You, S.-L. Chem. Sci.
2014, 5, 1059. (d) Kaiser, T. M.; Yang, J. Eur. J. Org. Chem. 2013, 3983.
For selected racemic benzylation and allylations, see: (e) Montgom-
ery, T. D.; Zhu, Y.; Kagawa, N.; Rawal, V. H. Org. Lett. 2013, 15, 1140.
(f) Zhang, X.; Liu, W.-B.; Wu, Q.-F.; You, S.-L. Org. Lett. 2013, 15,
3746.
(4) For chemoenzymatic studies of reverse prenylation, see (a)
Yin, W.-B.; Cheng, J.; Li, S.-M. Org. Biomol. Chem. 2009, 7, 2202. (b)
Yin, W.-B.; Xie, X.-L.; Matuschek, M.; Li, S.-M. Org. Biomol. Chem.
2010, 8, 1133. (c) Yin, W.-B.; Yu, X.; Xie, X.-L.; Li, S.-M. Org. Biomol.
Chem. 2010, 8, 2430. (d) Fan, A.; Li, S.-M. Adv. Synth. Catal. 2013, 355,
2659. (e) Luk, L. Y. P.; Qian, Q.; Tanner, M. E. J. Am. Chem. Soc. 2011,
133, 12342. (f) Rudolft, J. D.; Wang, H.; Poulter, C. D. J. Am. Chem.
Soc. 2013, 135, 1895.
(5) For a selected example of a Pd-catalyzed asymmetric construc-
tion of vicinal quaternary stereocenters, see: (a) Trost, B. M.; Osipov,
M. Angew. Chem. Int. Ed. 2013, 52, 9176. For selected examples of an
enantio- and diastereoselective Ir-catalyzed allylic alkylation to form
vicinal tertiary and all-carbon quaternary stereocenters, see (b) Liu,
W.-B.; Reeves, C. M.; Virgil, S. C.; Stoltz, B. M. J. Am. Chem. Soc.
2013, 135, 10626. (c) Liu, W.-B.; Reeves, C. M.; Stoltz, B. M. J. Am.
Chem. Soc. 2013, 135, 17298.
indoles with malonates or phenols as pendant nucleophiles gave a
complex mixture.
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(10) For selected examples, see: (a) Bhat, B.; Harrison, D. M. Tet-
rahedron Lett. 1986, 27, 5873. (b) Takase, S.; Itoh, Y.; Uchida, I.;
Tanaka, H.; Aoki, H. Tetrahedron 1986, 42, 5887. (c) Kawasaki, T.;
Shinada, M.; Ohzono, M.; Ogawa, A.; Terashima, R.; Sakamoto, M. J.
Org. Chem. 2008, 73, 5959. (d) Miller, K. A.; Tsukamoto, S.; Williams,
R. M. Nature Chem. 2009, 1, 63. (e) Takiguchi, S.; Iizuka, T.; Kumaku-
ra, Y.-s.; Murasaki, K.; Ban, N.; Higuchi, K.; Kawasaki, T. J. Org.
Chem. 2010, 75, 1126. (f) Adla, S. K.; Golz, G.; Jones, P. G.; Lindel, T.
Synthesis 2010, 2161.
(11) For selected examples, see: (a) Marsden, S. P.; Depew, K. M.;
Danishefsky, S. J. J. Am. Chem. Soc. 1994, 116, 11143. (b) Depew, K. M.;
Marsden, S. P.; Zatorska, D.; Zatorski, A.; Bornmann, W. G.; Dan-
ishefsky, S. J. J. Am. Chem. Soc. 1999, 121, 11953-11963. (c) Wang, Y.;
Kong, C.; Du, Y.; Song, H.; Zhang, D.; Qin, Y. Org. Biomol. Chem.
2012, 10, 2793. (d) Ideguchi, T.; Yamada, T.; Shirahata, T.; Hirose, T.;
Sugawara, A.; Kobayashi, Y.; Omura, S.; Sunazuka, T. J. Am. Chem.
Soc. 2013, 135, 12568.
(12) For selected reviews on the chemistry of hexahydro-
pyrrolo[2,3-b]indoles, see: (a) Crich, D.; Banerjee, A. Acc. Chem. Res.
2007, 40, 151. (b) Hino, T.; Nakagawa, M. Alkaloids 1989, 34, 1.
(13) Pd-catalyzed endo selective C3 allylation of tryptophan methyl
ester was reported, see Reference 2c.
(14) Biological activity: (a) Barrow, C. J.; Sun, H. H. J. Nat. Prod.
1994, 57, 471. Isolation: (b) Kimura, Y.; Hamasaki, T.; Nakajima, H.;
Isogai, A. Tetrahedron Lett. 1982, 23, 225. Chemoenzymatic synthesis:
(c) Bhat, B.; Harrison, D. M.; Lamont, H. M. Tetrahedron 1993, 49,
10663. (d) See also Reference 4a.
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(15) Isolation: (a) Kusano, M.; Sotoma, G.; Koshino, H.; Uzawa, J.;
Chijimatsu, M.; Fujioka, S.; Kawano, T.; Kimura, Y. J. Chem. Soc.,
Perkin Trans. 1 1998, 2823. Synthesis: (b) Matsumura, K.; Kitahara, T.
Heterocycles 2001, 54, 727.
(6) For selected enantio- and diastereoselective Ir-catalyzed allylic
substitution reactions from our group, see: (a) Schafroth, M. A.;
Sarlah, D.; Krautwald, S.; Carreira, E. M. J. Am. Chem. Soc. 2012, 134,
20276. (b) Krautwald, S.; Sarlah, D.; Schafroth, M. A.; Carreira, E. M.
Science 2013, 340, 1065. (c) O. F.; Kravina, A. G.; Carreira, E. M. An-
gew. Chem. Int. Ed. 2013, 52, 12166. (d) Krautwald, S.; Schafroth, M.
A.; Sarlah, D.; Carreira, E. M. J. Am. Chem. Soc. 2014, 136, 3020. (e)
On the basis of our previous studies, we believe the high regioselec-
tivity in the allylic displacement reactions can be explained by the
putative intermediate structure shown below. The highly congested
binding site leads to a binding mode in which positioning of the
dimethyl end group and attack by the nucleophile occur far from the
partially dissociated ligand.
(7) The use of KOt-Bu and Et3B for the activation of 1H-indoles
has been described, see: (a) Lin, A.; Yang, J.; Hashim, M. Org. Lett.
2013, 15, 1950. For related reports documenting the use of Et3B, see
Reference 2c and references therein.
(8) Diebolt, O.; Tricas, H.; Freixa, Z.; van Leeuwen, P. W. N. M.
ACS Catalysis 2013, 3, 128.
(9) (a) Both, 2,3-substituted and 3-unsubstituted indoles are also
suitable substrates: 2,3-dimethylindole gave the corresponding
indole imine in 55% yield and 5-methoxyindole afforded the C3
4
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