Organic Letters
Letter
Table 3. Use of a Substituted Allenyl Boronic Acid 39 or
Pinacolboronate 40
Present Addresses
†
Present address: RAFARM S.A., Pharmaceutical Industry, Agiou
Louka Street, Paiania, 19002 Attiki, Greece.
‡
Present address: European Chemicals Agency (ECHA), P.O.
Box 400, FI-00121 Helsinki, Finland.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
We thank the National Institutes of Health (Grant No. GM
5970) for financial support, and the University of Southern
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California for an LHI Moulton Fellowship and a Myronis
Scholarship to F.L.
REFERENCES
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(
1) (a) Petasis, N. A.; Zavialov, I. A. J. Am. Chem. Soc. 1997, 119, 445.
b) Petasis, N. A.; Goodman, A.; Zavialov, I. A. Tetrahedron 1997, 53,
(
1
6463. (c) Petasis, N. A.; Zavialov, I. A. J. Am. Chem. Soc. 1998, 120,
1
1798. (d) Petasis, N. A.; Patel, Z. D. Tetrahedron Lett. 2000, 41, 9607.
(e) Prakash, G. K. S.; Mandal, M.; Schweizer, S.; Petasis, N. A.; Olah, G.
A. Org. Lett. 2000, 2, 3173. (f) Petasis N. A.; Zavialov I. A. US Patent
6
,232,467, 2001. (g) Petasis, N. A.; Boral, S. Tetrahedron Lett. 2001, 42,
5
39. (h) Prakash, G. K. S.; Mandal, M.; Schweizer, S.; Petasis, N. A.;
Olah, G. A. J. Org. Chem. 2002, 67, 3718. (i) Petasis, N. A.; Butkevich, A.
N. J. Organomet. Chem. 2009, 694, 1747.
(2) Review: Petasis, N. A. Multicomponent Reactions with Organo-
boron Compounds. In Multicomponent Reactions; Zhu, J., Bienayme, H.,
Eds.; Wiley-VCH: New York, 2005; Chapter 7, pp 199−223.
(3) We reported a related stepwise process that we termed “boronic
acid Mannich reaction”, which involves the pre-condensation of amines
with formaldehyde followed by reaction with boronic acids. Petasis, N.
A.; Akritopoulou, I. Tetrahedron Lett. 1993, 34, 583.
(
4) This multicomponent reaction (MCR) is now being referred to in
the literature as the “Petasis reaction”.
5) For reviews, see: (a) Candeias, N. R.; Montalbano, F.; Cal, P. M. S.
(
7
a,8
D.; Gois, P. M. P. Chem. Rev. 2010, 110, 6169. (b) de Graaff, C.; Ruijter,
E.; Orru, R. V. A. Chem. Soc. Rev. 2012, 41, 3969. See also:
some time,
while the preformed tartrate derivatives were
shown to add readily to aldehydes and ketones in a practical and
enantioselective manner.
(c) Southwood, T. J.; Curry, M. C.; Hutton, C. A. Tetrahedron 2006,
8a−c
Despite their ability to undergo
8
6
2, 236. (d) Yamaoka, Y.; Miyabe, H.; Takemoto, Y. J. Am. Chem. Soc.
facile γ-intramolecular addition to aldehydes, the reported
chemistry demonstrates that allenyl boron compounds can also
add preferably to certain in situ adjacent iminium salts to produce
allenyl and alkynyl amines and amino acids. The products of this
one-step process are multifunctional allenyl and propargyl amine
derivatives, which are versatile and valuable building blocks for
2007, 129, 6686. (e) Muncipinto, G.; Moquist, P. N.; Schreiber, S. L.;
Schaus, S. E. Angew. Chem., Int. Ed. 2011, 50, 8172. (f) Han, W.-Y.; Wu,
Z.-J.; Zhang, X.-M.; Yuan, W.-C. Org. Lett. 2012, 14, 976.
(6) (a) Petasis, N. A.; Liepouri, F. Abstracts of the 229th ACS Meeting,
San Diego, CA, 2005; ORGN-483. (b) Petasis, N. A.; Liepouri, F.
Abstracts. Pacifichem; Honolulu, HI, 2005; Abstract 1813. (c) Petasis, N.
A.; Liepouri, F. Abstracts of the 232nd ACS Meeting, San Francisco, CA,
10
synthetic and medicinal applications.
2
006; ORGN-482.
7) (a) Furuta, K.; Ishiguro, M.; Haruta, R.; Ikeda, N.; Yamamoto, H.
Bull. Soc. Chem. Jpn. 1984, 57, 2768. (b) Poisson, J. F.; Normant, J. F. J.
Org. Chem. 2000, 65, 6553. (c) Hoffmann-Roder, A.; Krause, N. Angew.
In summary, we have developed a new, one-step, three-
component methodology to synthesize α-allenyl and α-propargyl
α-amino acids in a highly controllable way, just by selecting the
boron and amine components used. This chemistry has
interesting mechanistic features and can be used to generate
novel and potentially valuable molecules, particularly in light of
(
̈
Chem., Int. Ed. 2004, 43, 1196. (d) Schneider, U.; Sugiura, M.;
Kobayashi, S. Adv. Synth. Catal. 2006, 348, 323. (e) Brummond, K.;
DeForrest, J. Synthesis 2007, 795.
10
(8) (a) Haruta, R.; Ishiguro, M.; Ikeda, N.; Yamamoto, H. J. Am. Chem.
the growing synthetic utility of allenes and the popularity of
alkynes in click chemistry.
Soc. 1982, 104, 7667. (b) Ikeda, N.; Arai, I.; Yamamoto, H. J. Am. Chem.
Soc. 1986, 108, 483. (c) Wisniewska, H. M.; Jarvo, E. R. J. Org. Chem.
2
013, 78, 11629. (d) Vieira, E. M.; Haeffner, F.; Snapper, M. L.;
ASSOCIATED CONTENT
Supporting Information
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Hoveyda, A. H. Angew. Chem., Int. Ed. 2012, 51, 6618. (e) Huang, Y.-Y.;
Chakrabarti, A.; Morita, N.; Schneider, U.; Kobayashi, S. Angew. Chem.,
Int. Ed. 2011, 50, 11121.
(
(
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S
Experimental procedures and spectroscopic data for new
9) Established by NMR analysis of the crude reaction mixtures.
10)(a) Morita, N.;Krause, N. Org. Lett. 2004, 6, 4121. (b)Brummond,
K. M.; Curran, D. P.; Mitasev, B.; Fischer, S. J. Org. Chem. 2005, 70, 1745.
c) Ohno, H.; Mizutani, T.; Kadoh, Y.; Miyamura, K.; Tanaka, T. Angew.
Chem., Int. Ed. 2005, 44, 5113.
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AUTHOR INFORMATION
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Org. Lett. 2015, 17, 1628−1631