ORGANIC
LETTERS
2012
Vol. 14, No. 6
1416–1419
Ni- and Pd-Catalyzed Synthesis of
Substituted and Functionalized Allylic
Boronates
Ping Zhang, Ian A. Roundtree, and James P. Morken*
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill,
Massachusetts 02467, United States
Received January 19, 2012
ABSTRACT
Two highly efficient and convenient methods for the synthesis of functionalized and substituted allylic boronates are described. In one procedure,
readily available allylic acetates are converted to allylic boronates catalyzed by Ni/PCy3 or Ni/PPh3 complexes with high levels of stereoselectivity
and in good yields. Alternatively, the borylation can be accomplished with commercially available Pd catalysts [e.g., Pd2(dba)3, PdCl2, Pd/C],
starting with easily accessed allylic halides.
Organoboron reagents represent exceedingly versatile
building blocks for organic synthesis.1 Allylic boronates,2
in particular, are well-known for their additions to al-
dehydes,3 ketones,4 and imines,5 generating valuable homo-
allylic alcohols and amines, often with high levels of stereo-
control. More recently, allylic boronates have been used as
partners for cross-coupling reactions with aryl6 and allyl
electrophiles.7 Due to the importance of allylboronate
building blocks in synthetic organic chemistry, their synth-
esis has been the subject of many studies. Besides stoichio-
metric substitution reactions that involve allyllithium8 or
(1) For representative reviews: (a) Brown, H. C.; Singaram, B. Pure
Appl. Chem. 1987, 59, 879. (b) Miyaura, N.; Suzuki, A. Chem. Rev. 1995,
95, 2457. (c) Miyaura, N. Bull. Chem. Soc. Jpn. 2008, 81, 1535. (d)
Thomas, S. P.; French, R. M.; Jheengut, V.; Aggarwal, V. K. Chem. Rec.
2009, 9, 24.
(2) For represenative reviews: (a) Yamamoto, Y.; Asao, N. Chem.
Rev. 1993, 93, 2207. (b) Asymmetric Synthesis, 2nd ed.; Christmann, M.,
Braese, S., Eds.; Wiley-VCH: Weinheim, 2008. (c) Hugo, H.; Hall, D. Org.
React. 2008, 73, 1.
(3) For representative examples: (a) Kobayashi, S.; Endo, T.; Ueno,
M. Angew. Chem., Int. Ed. 2011, 50, 12262. (b) Jain, P.; Antilla, J. C. J.
Am. Chem. Soc. 2010, 132, 11884. (c) Rauniyar, V.; Zhai, H.; Hall, D. G.
J. Am. Chem. Soc. 2008, 130, 8481. (d) Gravel, M.; Lachance, H.; Lu, X.;
Hall, D. G. Synthesis 2004, 8, 1290. (e) Hoffmann, R. W. Angew. Chem.,
Int. Ed. 1987, 26, 489.
(4) For a review, see: (a) Marek, I.; Sklute, G. Chem. Commun. 2007,
1683. For representative examples: (b) Fandrick, K. R.; Fandrick,
D. R.; Gao, J. J.; Reeves, J. T.; Tan, Z. T.; Li, W.; Song, J. J.; Lu, B.; Yee,
N. K; Senanayake, C. H. Org. Lett. 2010, 12, 3748. (c) Lou, S.; Moquist.,
P. N.; Schaus, S. E. J. Am. Chem. Soc. 2006, 128, 12660. (d) Wada, R.;
Oisaki, K.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 2004, 126, 8910.
(5) For a review, see: (a) Ramadhar, T. R.; Batey, R. A. Synthesis
2011, 9, 1321. For representative examples: (b) Viera, E. M.; Snapper,
M. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2011, 133, 3332. (c) Lou, L.;
Moquist, P. N.; Schaus, S. E. J. Am. Chem. Soc. 2006, 129, 15398. (d)
Wada, R.; Shibaguichi, T.; Makino, S.; Oisaki, K.; Kanai, M.; Shiba-
saki, M. J. Am. Chem. Soc. 2006, 128, 7687. (e) Wu, T. R.; Chong, J. M.
J. Am. Chem. Soc. 2006, 128, 9646. (f) Itsuno, S.; Watanabo, K.; Ito, K.;
El-Shehawy, A. A.; Sarhan, A. A. Angew. Chem., Int. Ed. 1997, 36, 109.
(6) For representative examples: (a) Yamamoto, Y.; Takada, S.;
Miyaura, N. Chem. Lett. 2006, 35, 704. (b) Yamamoto, Y.; Takada, S.;
Miyaura, N. Chem. Lett. 2006, 35, 1368. (c) Yamamoto, Y.; Takada,
S.; Miyaura, N. Organometallics 2009, 28, 152. (d) Gerbino, D. C.;
Mandolesi, S. D.; Schmalz, H.; Podesta, J. C. Eur. J. Org. Chem. 2009,
3964. (e) Dai, Q.; Xie, X.; Xu, S.; Ma, D.; Tang, S.; She, X. Org. Lett.
2011, 13, 2302.
ꢀ
(7) (a) Zhang, P.; Brozek, L. A.; Morken, J. P. J. Am. Chem. Soc.
2010, 132, 10686. (b) Zhang, P.; Le, H.; Kyne, R. E.; Morken, J. P. J. Am.
Chem. Soc. 2011, 133, 9716. (c) Brozek, L. A.; Ardolino, M. J.; Morken,
J. P. J. Am. Chem. Soc. 2011, 133, 16778. (d) Flegeau, E. F.; Schneider,
ꢀ
U.; Kobayashi, S. Chem.;Eur. J. 2009, 15, 12247. (e) Jimenez-Aquino,
A.; Flegeau, E. F.; Schneider, U.; Kobayashi, S. Chem. Commun. 2011,
47, 9456.
(8) For representative examples: Brown, H. C.; Rangaishenvi, M. V.
Tetrahedron Lett. 1990, 31, 7113.
(9) For representative examples: (a) Roush, W. R.; Walts, A. E.;
Hoong, L. K. J. Am. Chem. Soc. 1985, 107, 8186. (b) Brown, H. C.;
Racherla, U. S.; Pellechia, P. J. J. Org. Chem. 1990, 55, 1868.
r
10.1021/ol3001552
Published on Web 02/29/2012
2012 American Chemical Society