Organic Letters
Letter
Quarternary Centers. Org. Lett. 2016, 18, 3906. (l) Laugeois, M.;
ACKNOWLEDGMENTS
■
́
Ling, J.; Ferard, C.; Michelet, V.; Ratovelomanana-Vidal, V.; Vitale,
We thank the National Key R&D Program of China
(2016YFA0202900) and NSFC (21821002, 21572252) for
generous financial support.
M. R. Palladium(0)-Catalyzed Dearomative [3 + 2] Cycloaddition of
3-Nitroindoles with Vinylcyclopropanes: an Entry to Stereodefined
2,3-Fused Cyclopentannulated Indoline Derivatives. Org. Lett. 2017,
19, 2266. (m) Gao, R.-D.; Ding, L.; Zheng, C.; Dai, L.-X.; You, S.-L.
Palladium(0)-Catalyzed Intermolecular Asymmetric Allylic Dearoma-
tization of Polycyclic Indoles. Org. Lett. 2018, 20, 748. (n) Trost, B.
M.; Bai, W.-J.; Hohn, C.; Bai, Y.; Cregg, J. J. Palladium-Catalyzed
Asymmetric Allylic Alkylation of 3-Substituted 1H-Indoles and
Tryptophan Derivatives with Vinylcyclopropanes. J. Am. Chem. Soc.
2018, 140, 6710.
REFERENCES
■
(1) For selected reviews on Pd-catalyzed allylic substitution
reactions, see: (a) Consiglio, G.; Waymouth, R. M. Enantioselective
Homogeneous Catalysis Involving Transition-Metal-Allyl Intermedi-
ates. Chem. Rev. 1989, 89, 257. (b) Trost, B. M. Pd Asymmetric
Allylic Alkylation (AAA). A Powerful Synthetic Tool. Chem. Pharm.
Bull. 2002, 50 (1), 1. (c) Miyabe, H.; Takemoto, Y. Regio- and
Stereocontrolled Palladium- or Iridium-Catalyzed Allylation. Synlett
2005, 11, 1641. (d) You, S.-L.; Dai, L.-X. Enantioselective Palladium-
Catalyzed Decarboxylative Allylic Alkylations. Angew. Chem., Int. Ed.
2006, 45, 5246. (e) Trost, B. M.; Machacek, M. R.; Aponick, A.
Predicting the Stereochemistry of Diphenylphosphino Benzoic Acid
(DPPBA)-Based Palladium-Catalyzed Asymmetric Allylic Alkylation
Reactions: A Working Model. Acc. Chem. Res. 2006, 39, 747.
(f) Mohr, J. T.; Stoltz, B. M. Enantioselective Tsuji Allylations. Chem.
- Asian J. 2007, 2, 1476. (g) Lu, Z.; Ma, S. Metal-Catalyzed
Enantioselective Allylation in Asymmetric Synthesis. Angew. Chem.,
Int. Ed. 2008, 47, 258. (h) Trost, B. M.; Zhang, T.; Sieber, J. D.
Catalytic Asymmetric Allylic Alkylation Employing Heteroatom
Nucleophiles: A Powerful Method for C-X Bond Formation. Chem.
Sci. 2010, 1, 427. (i) Trost, B. M. Pd- and Mo-Catalyzed Asymmetric
Allylic Alkylation. Org. Process Res. Dev. 2012, 16, 185. (j) Liu, Y.;
Han, S.-J.; Liu, W.-B.; Stoltz, B. M. Catalytic Enantioselective
Construction of Quaternary Stereocenters: Assembly of Key Building
Blocks for the Synthesis of Biologically Active Molecules. Acc. Chem.
Res. 2015, 48, 740. (k) Grange, R. L.; Clizbe, E. A.; Evans, P. A.
Recent Developments in Asymmetric Allylic Amination Reactions.
Synthesis 2016, 48, 2911. (l) Wang, Y.-N.; Lu, L.-Q.; Xiao, W.-J. Non-
Bonding Interactions Enable the Selective Formation of Branched
Products in Palladium-Catalyzed Allylic Substitution Reactions. Chem.
- Asian J. 2018, 13, 2174.
(2) For selected reviews on dearomatization reactions, see:
(a) Zhuo, C.-X.; Zhang, W.; You, S.-L. Catalytic Asymmetric
Dearomatization Reactions. Angew. Chem., Int. Ed. 2012, 51, 12662.
(b) Ding, Q.; Zhou, X.; Fan, R. Recent Advances in Dearomatization
of Heteroaromatic Compounds. Org. Biomol. Chem. 2014, 12, 4807.
(c) Zheng, C.; You, S.-L. Catalytic Asymmetric Dearomatization by
Transition-Metal Catalysis: A Method for Transformations of
Aromatic Compounds. Chem. 2016, 1, 830. (d) Wu, W.-T.; Zhang,
L.; You, S.-L. Recent Progress on Gold-catalyzed Dearomatization
Reactions. Huaxue Xuebao 2017, 75, 419. For selected recent
examples, see: (e) Kimura, M.; Futamata, M.; Mukai, R.; Tamaru, Y.
Pd-Catalyzed C3-Selective Allylation of Indoles with Allyl Alcohols
Promoted by Triethylborane. J. Am. Chem. Soc. 2005, 127, 4592.
(f) Trost, B. M.; Quancard, J. Palladium-Catalyzed Enantioselective
C-3 Allylation of 3-Substituted-1H-Indoles Using Trialkylboranes. J.
Am. Chem. Soc. 2006, 128, 6314. (g) Nemoto, T.; Ishige, Y.; Yoshida,
M.; Kohno, Y.; Kanematsu, M.; Hamada, Y. Novel Method for
Synthesizing Spiro[4.5]cyclohexadienones through a Pd-Catalyzed
Intramolecular ipso-Friedel-Crafts Allylic Alkylation of Phenols. Org.
Lett. 2010, 12, 5020. (h) Trost, B. M.; Ehmke, V.; O’Keefe, B. M.;
Bringley, D. A. Palladium-Catalyzed Dearomative Trimethylene-
methane Cycloaddition Reactions. J. Am. Chem. Soc. 2014, 136,
8213. (i) Montgomery, T. D.; Nibbs, A. E.; Zhu, Y.; Rawal, V. H.
Rapid Access to Spirocyclized Indolenines via Palladium-Catalyzed
Cascade Reactions of Tryptamine Derivatives and Propargyl
Carbonate. Org. Lett. 2014, 16, 3480. (j) Nibbs, A. E.;
Montgomery, T. D.; Zhu, Y.; Rawal, V. H. Access to Spirocyclized
Oxindoles and Indolenines via Palladium-Catalyzed Cascade Re-
actions of Propargyl Carbonates with 2-Oxotryptamines and Trypt-
amines. J. Org. Chem. 2015, 80, 4928. (k) Gao, S.; Wu, Z.; Fang, X.;
Lin, A.; Yao, H. Palladium-Catalyzed Dearomative Allylic Alkylation
of Indoles with Alkynes to Synthesize Indolenines with C3-
(3) For selected examples, see: (a) Garraffo, H. M.; Spande, T. F.;
Daly, J. W.; Baldessari, A.; Gros, E. G. Alkaloids from Bufonid Toads
(Melanophryniscus): Decahydroquinolines, Pumiliotoxins and Ho-
mopumiliotoxins, Indolizidines, Pyrrolizidines, and Quinolizidines. J.
Nat. Prod. 1993, 56, 357. (b) Negoro, T.; Murata, M.; Ueda, S.;
Fujitani, B.; Ono, Y.; Kuromiya, A.; Komiya, M.; Suzuki, K.;
Matsumoto, J.-i. Novel, Highly Potent Aldose Reductase Inhibitors:
(R)-(−)-2-(4-Bromo-2-fluorobenzyl)-1,2,3,4-tetrahydropyrrolo[1,2-
a]pyrazine-4-spiro-3′-pyrrolidine-1,2’,3,5′-tetrone (AS-3201) and Its
Congeners. J. Med. Chem. 1998, 41, 4118. (c) Chen, Y.-L.; Fang, K.-
C.; Shen, J.-Y.; Hsu, S.-L.; Tzeng, C.-C. Synthesis and Antibacterial
Evaluation of Certain Quinolone Derivatives. J. Med. Chem. 2001, 44,
2374. (d) Kariba, R. M.; Houghton, P. J.; Yenesew, A. Antimicrobial
Activities of a New Schizozygane Indoline Alkaloid from Schizozygia
coffaeoides and the Revised Structure of Isoschizogaline. J. Nat. Prod.
2002, 65, 566. (e) Likhosherstov, A. M.; Filippova, O. V.; Peresada, V.
P.; Kryzhanovskii, S. A.; Vititnova, M. B.; Kaverina, N. V.; Reznikov,
K. M. Azacycloalkanes. XXXIV. Synthesis and Antiarrhythmic Activity
of 2-(2’-R-2’-Hydroxyethyl)-1,2,3,4-tetra-hydro-pyrrolo-[1,2-a]-
pyrazines. Pharm. Chem. J. 2003, 37, 6. (f) Ahmed, E.; Briseno, A.
L.; Xia, Y.; Jenekhe, S. A. High Mobility Single-Crystal Field-Effect
Transistors from Bisindoloquinoline Semiconductors. J. Am. Chem.
Soc. 2008, 130, 1118. (g) Mai, A.; Valente, S.; Meade, S.; Carafa, V.;
Tardugno, M.; Nebbioso, A.; Galmozzi, A.; Mitro, N.; Fabiani, E. D.;
Altucci, L.; Kazantsev, A. Study of 1,4-Dihydropyridine Structural
Scaffold: Discovery of Novel Sirtuin Activators and Inhibitors. J. Med.
Chem. 2009, 52, 5496. (h) Wang, Y.; Ai, J.; Wang, Y.; Chen, Y.; Wang,
L.; Liu, G.; Geng, M.; Zhang, A. Synthesis and c-Met Kinase
Inhibition of 3,5-Disubstituted and 3,5,7-Trisubstituted Quinolines:
Identification of 3−(4-Acetylpiperazin-1-yl)-5-(3-nitrobenzylamino)-
7-(trifluoromethyl)quinoline as a Novel Anticancer Agent. J. Med.
Chem. 2011, 54, 2127. (i) Southgate, E. H.; Pospech, J.; Fu, J.;
Holycross, D. R.; Sarlah, D. Dearomative Dihydroxylation with
Arenophiles. Nat. Chem. 2016, 8, 922. (j) Kaptein, S. J. F.; Neyts, J.
Towards Antiviral Therapies for Treating Dengue Virus Infections.
Curr. Opin. Pharmacol. 2016, 30, 1. (k) Bhattarai, D.; Xu, X.; Lee, K.
Hypoxia-Inducible Factor-1 (HIF-1) Inhibitors from the Last Decade
(2007 to 2016): A “Structure-Activity Relationship” Perspective. Med.
Res. Rev. 2018, 38, 1404.
(4) For selected recent examples, see: (a) Gutsulyak, D. V.; van der
Est, A.; Nikonov, G. I. Facile Catalytic Hydrosilylation of Pyridines.
Angew. Chem., Int. Ed. 2011, 50, 1384. (b) Arrowsmith, M.; Hill, M.
̈
S.; Hadlington, T.; Kociok-Kohn, G.; Weetman, C. Magnesium-
Catalyzed Hydroboration of Pyridines. Organometallics 2011, 30,
5556. (c) Zurro, M.; Asmus, S.; Beckendorf, S.; Mu
̈
ck-Lichtenfeld, C.;
Mancheno, O. G. Chiral Helical Oligotriazoles: New Class of Anion-
̃
Binding Catalysts for the Asymmetric Dearomatization of Electron-
Deficient N-Heteroarenes. J. Am. Chem. Soc. 2014, 136, 13999.
(d) Zhao, X.; Liu, X.; Mei, H.; Guo, J.; Lin, L.; Feng, X. Asymmetric
Dearomatization of Indoles through a Michael/Friedel-Crafts-Type
Cascade to Construct Polycyclic Spiroindolines. Angew. Chem., Int. Ed.
2015, 54, 4032. (e) Shao, W.; Li, H.; Liu, C.; Liu, C.-J.; You, S.-L.
Copper-Catalyzed Intermolecular Asymmetric Propargylic Dearoma-
tization of Indoles. Angew. Chem., Int. Ed. 2015, 54, 7684. (f) James,
M. J.; Grant, N. D.; O’Brien, P.; Taylor, R. J. K.; Unsworth, W. P.
Catalytic Dearomatization Approach to Quinolizidine Alkaloids: Five
Step Total Synthesis of ( )-Lasubine II. Org. Lett. 2016, 18, 6256.
D
Org. Lett. XXXX, XXX, XXX−XXX