Organic Letters
Letter
to isoindoles.6a After eliminating the siloxy group, the final
product isoquinoline was generated.
As indicated in Table 1 and Scheme 2, the bulkier base catalyst
was beneficial to avoid the formation of lactam, and the presence
of electron-donating groups at the N-benzylic group were
helpful to promote the tandem reaction process. These two
observations were in good accordance with the proposed
involvement of intramolecular α-carbanion additions.
In summary, we have developed an alkoxide-catalyzed tandem
reaction of nucleophilic rearrangement and hydrosilylation of
readily available phthalimides to isoquinolines. With TMSOK
(10 mol %) as the catalyst and (EtO)2MeSiH as the reductant,
various cyclic imides were effectively converted to the
corresponding 3-aryl isoquinolines in moderate to good yields.
This catalytic protocol showed a wide functional tolerance of
halogens, naphthalene rings, and aromatic heterocycles.
5415. (b) Wang, Z.; Cheng, M.; Wu, P.; Wei, S.; Sun, J. Org. Lett. 2006,
8, 3045−3048. (c) Jiang, Y.; Chen, X.; Zheng, Y.; Xue, Z.; Shu, C.;
Yuan, W.; Zhang, X. Angew. Chem., Int. Ed. 2011, 50, 7304−7307.
(d) Medina, C.; Carter, K. P.; Miller, M.; Clark, T. B.; O’Neil, G. W. J.
́
Org. Chem. 2013, 78, 9093−9101. (e) Fernandez-Salas, J. A.; Manzini,
S.; Nolan, S. P. Chem. Commun. 2013, 49, 9758−9760. (f) Bornschein,
C.; Werkmeister, S.; Junge, K.; Beller, M. New J. Chem. 2013, 37, 2061−
2065. (g) Kawanami, Y.; Yuasa, H.; Toriyama, F.; Yoshida, S.-i.; Baba,
T. Catal. Commun. 2003, 4, 455−459. (h) Revunova, K.; Nikonov, G. I.
Chem. - Eur. J. 2014, 20, 839−845. (i) Xie, W.; Zhao, M.; Cui, C.
Organometallics 2013, 32, 7440−7444. (j) Mamillapalli, N. C.; Sekar, G.
́
́
RSC Adv. 2014, 4, 61077−61085. (k) Courtemanche, M.-A.; Legare,
́
M.-A.; Rochette, E.; Fontaine, F.-G. Chem. Commun. 2015, 51, 6858−
6861.
(5) (a) Kira, M.; Sato, K.; Sakurai, H. J. Org. Chem. 1987, 52, 948−
949. (b) Fedorov, A.; Toutov, A. A.; Swisher, N. A.; Grubbs, R. H.
Chem. Sci. 2013, 4, 1640−1645.
(6) (a) Volkov, A.; Tinnis, F.; Adolfsson, H. Org. Lett. 2014, 16, 680−
683. (b) Ding, G.; Wu, X.; Jiang, L.; Zhang, Z.; Xie, X. Org. Lett. 2017,
19, 6048−6051.
ASSOCIATED CONTENT
* Supporting Information
■
S
(7) Kavitha, K.; Shanthi Praveena, K. S.; Venkat Shivaji Ramarao, E.
V.; Sreenivasa Murthy, N. Y.; Pal, S. Curr. Org. Chem. 2016, 20, 1955−
2001.
The Supporting Information is available free of charge on the
̈
(8) (a) Das, S.; Addis, D.; Knopke, L. R.; Bentrup, U.; Junge, K.;
Bru
̈
ckner, A.; Beller, M. Angew. Chem., Int. Ed. 2011, 50, 9180−9184.
Detailed optimization data for the reaction conditions,
experimental procedures, and product characterization
(b) Ding, G.; Li, C.; Shen, Y.; Lu, B.; Zhang, Z.; Xie, X. Adv. Synth.
Catal. 2016, 358, 1241−1250.
(9) (a) Hill, J. H. M. J. Org. Chem. 1965, 30, 620−622. (b) Kapatsina,
E.; Lordon, M.; Baro, A.; Laschat, S. Synthesis 2008, 2008, 2551−2560.
(10) (a) Bentley, K. W. Nat. Prod. Rep. 2006, 23, 444−463.
(b) Durola, F.; Sauvage, J.-P.; Wenger, O. S. Chem. Commun. 2006,
171−173. (c) Khadka, D. B.; Cho, W.-J. Bioorg. Med. Chem. 2011, 19,
724−734. (d) Qing, Z.-X.; Yang, P.; Tang, Q.; Cheng, P.; Liu, X.-B.;
Zheng, Y.-j.; Liu, Y.-S.; Zeng, J.-G. Curr. Org. Chem. 2017, 21, 1920−
1934.
(11) (a) Balasubramanian, M.; Keay, J. G. Pyridines and their benzo
derivatives: applications. In Comprehensive Heterocyclic Chemistry II;
McKillop, A. E., Katrizky, A. R., Rees, C. W., Scrivem, E. F. V., Eds.;
Elsevier: Oxford, 1996; Vol. 5, pp 245−300. (b) Whaley, W. M.;
Govindachari, T. R. Preparation of 3,4-dihydroisoquinolines and
related compounds by the Bischler-Napieralski reaction. In Organic
Reactions; Roger, A., Ed.; John Wiley and Sons, Inc.: New York, 1951;
Vol. VI, pp 74−150. (c) Whaley, W. M.; Govindachari, T. R. The Pictet-
Spengler synthesis of tetrahydroisoquinolines and related compounds.
In Organic Reactions; Roger, A., Eds.; John Wiley and Sons, Inc.: New
York, 1951; Vol. VI, pp 151−190. (d) Gensler, W. J. Synthesis of
isoquinolines by the Pomeranz−Fritsch Reaction. In Organic Reactions;
Roger, A., Ed.; John Wiley and Sons, Inc.: New York, 1951; Vol. VI, pp
191−206.
AUTHOR INFORMATION
■
Corresponding Author
ORCID
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank the National Natural Science Foundation of China
(No. 21672143) and the Interdisciplinary Program of Shanghai
Jiao Tong University (YG2017MS26) for financial support.
REFERENCES
■
(1) (a) Ojima, I.; Li, Z.; Zhu, J. The Chemistry of Organic Silicon
Compounds; John Wiley & Sons, Ltd: West Sussex, 1998; Vol. 2, pp
(12) For examples of transition-metal-catalyzed cyclization: (a) Dai,
G.; Larock, R. C. Org. Lett. 2001, 3, 4035−4038. (b) Lage, S.; Martínez-
Estíbalez, U.; Sotomayor, N.; Lete, E. Adv. Synth. Catal. 2009, 351,
2460−2468. (c) Roy, S.; Roy, S.; Neuenswander, B.; Hill, D.; Larock, R.
C. J. Comb. Chem. 2009, 11, 1061−1065. (d) Liu, C.-C.; Parthasarathy,
K.; Cheng, C.-H. Org. Lett. 2010, 12, 3518−3521. (e) Zheng, D.; Li, S.;
Wu, J. Org. Lett. 2012, 14, 2655−2657. (f) Huang, P.; Yang, Q.; Chen,
Z.; Ding, Q.; Xu, J.; Peng, Y. J. Org. Chem. 2012, 77, 8092−8098.
(g) Jiang, H.; Cheng, Y.; Wang, R.; Zhang, Y.; Yu, S. Chem. Commun.
2014, 50, 6164−6167. (h) He, R.; Huang, Z.; Zheng, Q.; Wang, C.
Angew. Chem., Int. Ed. 2014, 53, 4950−4953. (i) Li, J.; Tang, M.; Zang,
L.; Zhang, X.; Zhang, Z.; Ackermann, L. Org. Lett. 2016, 18, 2742−
́
1687−1792. (b) Díez-Gonzalez, S.; Nolan, S. P. Org. Prep. Proced. Int.
2007, 39, 523−559. (c) Addis, D.; Das, S.; Junge, K.; Beller, M. Angew.
Chem., Int. Ed. 2011, 50, 6004−6011. (d) Revunova, K.; Nikonov, G. I.
Dalton Trans. 2015, 44, 840−866. (e) Herrera, R. P. Top. Curr. Chem.
2016, 374, 2364−8961.
(2) (a) Gronert, S.; Glaser, R.; Streitwieser, A. J. Am. Chem. Soc. 1989,
111, 3111−3117. (b) Larson, G. L.; Fry, J. L. Org. React. 2008, 71, 1−
737. (c) Du, X.; Huang, Z. ACS Catal. 2017, 7, 1227−1243.
(3) For reviews: (a) Nagai, Y. Org. Prep. Proced. Int. 1980, 12, 13−48.
(b) Enthaler, S. ACS Catal. 2013, 3, 150−158. (c) Chakraborty, S.;
Bhattacharya, P.; Dai, H.; Guan, H. Acc. Chem. Res. 2015, 48, 1995−
́
2003. (d) Merel, D. S.; Do, M. L. T.; Gaillard, S.; Dupau, P.; Renaud, J.-
́
2745. (j) Qiu, G.; Wu, J. Chem. Rec. 2016, 16, 19−34. (k) Mora-Rado,
L. Coord. Chem. Rev. 2015, 288, 50−68. (e) Li, B.; Sortais, J.-B.; Darcel,
C. RSC Adv. 2016, 6, 57603−57625. (f) Volkov, A.; Tinnis, F.;
Slagbrand, T.; Trillo, P.; Adolfsson, H. Chem. Soc. Rev. 2016, 45, 6685−
6697. (g) Lipke, M. C.; Liberman-Martin, A. L.; Tilley, T. D. Angew.
Chem., Int. Ed. 2017, 56, 2260−2294. (h) Meng, W.; Feng, X.; Du, H.
Acc. Chem. Res. 2018, 51, 191−201.
́
H.; Bialy, L.; Czechtizky, W.; Mendez, M.; Harrity, J. P. A. Angew.
Chem., Int. Ed. 2016, 55, 5834−5836.
(13) Wang, S.; Golec, J.; Miller, W.; Milutinovic, S.; Folkes, A.;
Williams, S.; Brooks, T.; Hardman, K.; Charlton, P.; Wren, S.; Spencer,
J. Bioorg. Med. Chem. Lett. 2002, 12, 2367−2370.
(4) For examples of Lewis base-catalyzed hydrosilylation of carbonyl
compounds: (a) Fujita, M.; Hiyama, T. J. Org. Chem. 1988, 53, 5405−
D
Org. Lett. XXXX, XXX, XXX−XXX