ORGANIC
LETTERS
2011
Vol. 13, No. 19
5314–5317
Addition of Arylboronic Acids to
Arylpropargyl Alcohols en Route to
Indenes and Quinolines
Jane Panteleev, Richard Y. Huang, Erica K. J. Lui, and Mark Lautens*
Department of Chemistry, University of Toronto, 80 St. George Street, Toronto,
Ontario, Canada, M5S 3H6
Received August 10, 2011
ABSTRACT
A regio- and stereoselective rhodium-catalyzed synthesis of trisubstituted allylic alcohols is described. The utility of these synthons is
demonstrated in a convenient synthesis of indenes and quinolines.
Carbometalation of easily accessible propargylic alco-
hols provides a good access point to substituted allylic
alcohols.1,2 Various metals can promote arylation and
alkylation of internal alkynes, but most protocols require
the use of highly reactive and sensitive organometallic
reagents.2 Rhodium-catalyzed arylation of alkynes with
boronic acids bypasses this obstacle.3,4 Since the report of
this reaction by Hayashi and our work on unsymmetrical
alkynes,4,5 some applications of this chemistry have been
reported; however unprotected propargylic alcohols are
not well studied.3d In this work we describe a rhodium-
catalyzed arylation of aryl-substituted propargylic alco-
hols, which takes place in high yields and regio- and
stereoselectivity. Furthermore, we show that the resulting
allylic alcohols can be used in a one-step synthesis of
indenes and as an access point to quinolines, both of which
are useful classes of molecules.6,7
(1) For reviews on carbometalation of alkynes, see: (a) Normant,
J. F.; Alexakis, A. Synthesis 1981, 841–870. (b) Hoveyda, A. H.; Evans,
D. A.; Fu, G. C. Chem. Rev. 1993, 93, 1307–1370. (c) Fallis., A. G.;
Forgione, P. Tetrahedron 2001, 57, 5899–5913. (d) Flynn, A. B.; Ogilvie,
W. W. Chem. Rev. 2007, 107, 4698–4745.
(2) Synthesis of allylic alcohols from propargylic alkynes - From
propargylic alcohols and nucleophiles: (a) Tessier, P. E.; Penwell, A. J.;
Souza, F. E. S.; Fallis, A. G. Org. Lett. 2003, 5, 2989–2992. (b) Tessier,
P. E.; Nguyen, N.; Cly, M. D.; Fallis, A. G. Org. Lett. 2005, 7, 767–770.
(c) Denmark, S. E.; Pan., W. Org. Lett. 2003, 5, 1119–1122. (d) Zhang,
X.; Lu, Z.; Fu, C.; Ma, S. Org. Biomol. Chem. 2009, 7, 3258–3263. (e) Oh,
C. H.; Jung, H. H.; Kim, K. S.; Kim., N. Angew. Chem., Int. Ed. 2003, 42,
805–808. (f) Gupta, A. K.; Kim, K. S.; Oh, C. H. Synlett 2005, 457–460.
From propargylic alcohols and aryl halides: (g) Durandetti, M.; Hard-
Although rhodium-catalyzed arylation of internal al-
kynes has the potential to be useful, the regioselectivity is
ꢀ
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(h) Yanada, R.; Obika, S.; Inokuma, T.; Yanada, K.; Yamashita, M.;
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Fabrizi, G.; Moro, L.; Pace, P. Synlett 1977, 1367–1370. (j) Arcadi, A.;
Cacchi, S.; Fabrizi, G.; Marinelli, F.; Pace, P. Eur. J. Org. Chem. 2000,
4099–4108. Selected examples of alternative reactivity of propargylic
alcohols and boronic acids: (k) Yoshida, M.; Gotou, T.; Ihara, M.
Tetrahedron Lett. 2004, 45, 5573–5575. (l) Dheur, J.; Sauthier, M.;
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(3) Hayashi, T.; Inoue, K.; Tamiguchi, N.; Ogasawara, M. J. Am.
Chem. Soc. 2001, 123, 9918–9919. (b) Matsuda, T.; Makino, M.;
Murakami, M. Angew. Chem., Int. Ed. 2005, 44, 4608–4611. (c) Harada,
Y.; Nakanishi, J.; Fujihara, H.; Tobisu, M.; Fukumoto, U.; Chatani, N.
J. Am. Chem. Soc. 2007, 129, 5766–5771. (d) Acardi, A.; Aschi, M.;
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(4) For reviews on reactions featuring rhodium catalyzed arylation of
alkynes, see: (a) Miura, T.; Murakami, M. Chem. Commun. 2007, 217–
224. (b) Youn, S. W. Eur. J. Org. Chem. 2009, 2597–2605.
(5) (a) Lautens, M.; Yoshida, M. Org. Lett. 2002, 4, 123–125. (b)
Lautens, M.; Yoshida, M. J. Org. Chem. 2003, 68, 762–769. (c) Tsui,
G. T.; Lautens, M. Angew. Chem., Int. Ed. 2010, 49, 8938–8941.
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Kawata, A.; Shouho, M.; Takai, K. Pure Appl. Chem. 2008, 80, 1149–
1154. (b) Enders, M.; Baker, R. W. Curr. Org. Chem. 2006, 10, 937–953.
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10.1021/ol202176g
Published on Web 09/14/2011
2011 American Chemical Society