We have to point out that this reaction seems to be limited
to the utilization of Type I olefins (in the Grubbs olefin
classification)6 as allyl acetate and methyl-2-pentene do not
produce the corresponding CM product. The addition of
various amines to intermediate A was realized, and excellent
yields in the corresponding substituted acrylamides were
obtained (65-81%) (Table 3). It is worth noting that when
cheap amines were utilized, a large excess of the amine was
introduced in the reaction mixture (Table 3, entries 4-5).
In the case of more valuable amines, 1.6 equiv of amine
was added to the reaction media as well as an additive, K3PO4
(3.8 equiv)7 (Table 3, entries 1, 2, 6, and 78). When amine
hydrochlorides were used, including Weinreb amine hydro-
chloride,9 the best results in substituted acrylamides were
obtained when N-methylmorpholine was introduced in the
reaction media (Table 3, entries 3, 8, and 9).
The CM products resulting from acryloyl chloride 1 and
olefin 2 can also be trapped with nucleophiles other than amines
such as allylic and propargylic alcohols. The corresponding
esters 3m and 3n were formed in good yields (63-65%) at 0
°C in the presence of pyridine (Table 3, entries 10 and 11).
Sodium azide is also able to react with intermediate A as
the azido derivative 3o was formed in 63% yield (Table 3,
entry 12). It is worth noting that 9 is unstable and cannot be
used to prepare 3o (Scheme 2);10 the latter can be a useful
intermediate for the preparation of vinyl isocyanates.11
Table 3. Addition of Various Nucleophilesa
Scheme 2
In conclusion, a very simple one-pot process involving a CM
between acryloyl chloride and terminal olefins followed by the
addition of nucleophiles leads to a diversity of functionalized
R,ꢀ-unsaturated carbonyl compounds in good yields. Extension
to other nucleophiles and the use of this one-pot sequence to
synthesize a library of biologically active compounds is
underway in our laboratory and will be reported in due course.
Supporting Information Available: General procedure
for the cross-metathesis reactions and 1H NMR and 13C NMR
spectra of all new compounds. This material is available free
OL9021386
(3) (a) Garber, S. B.; Kingsbury, J. S.; Gray, B. L.; Hoveyda, A. H.
J. Am. Chem. Soc. 2000, 122, 8168. (b) Gessler, S.; Randl, S.; Blechert, S.
Tetrahedron Lett. 2000, 41, 9973.
(4) Grela, K.; Harutyunyan, S.; Michrowska, A. Angew. Chem., Int. Ed.
2002, 41, 4038. (b) Michrowska, A.; Bujok, R.; Harutyunyan, S.; Sashuk,
V.; Dolgonos, G.; Grela, K. J. Am. Chem. Soc. 2004, 126, 9318. (c) Bieniek,
M.; Bujok, R.; Cabaj, M.; Lugan, N.; Lavigne, G.; Arlt, D.; Grela, K. J. Am.
Chem. Soc. 2006, 128, 13652.
(5) Choi, T.-L.; Chatterjee, A. K.; Grubbs, R. H. Angew. Chem., Int.
Ed. 2001, 40, 1277.
(6) Chatterjee, A. K.; Choi, T.-L.; Sanders, D.; Grubbs, R. H. J. Am.
Chem. Soc. 2003, 125, 11360.
(7) Zhang, L.; Wang, X. J.; Wang, J.; Grinberg, N.; Krishnamurthy,
D. K.; Senanayake, C. H. Tetrahedron Lett. 2009, 22, 2964.
(8) Myers, A. G.; Yang, B. H.; Chen, H.; McKinstry, L.; Kopecky, D. J.;
Gleason, J. L. J. Am. Chem. Soc. 1997, 119, 6496.
(9) Nahm, S.; Weinreb, S. M. Tetrahedron Lett. 1981, 22, 3815.
(10) 12 must be kept in solution; see: Wieber, J. M.; Hegedus, L. S.;
Akermark, B.; Michalson, E. T. J. Org. Chem. 1989, 54, 4649.
(11) (a) Stefanuti, I.; Smith, S. A.; Taylor, R. J. K. Tetrahedron Lett.
2000, 41, 3735. (b) Kondo, T.; Tanaka, A.; Kotachi, S.; Watanabe, Y.
J. Chem. Soc., Chem. Commun. 1995, 413. (c) Ogawa, T.; Kiji, T.; Hayami,
K.; Suzuki, H. Chem. Lett. 1991, 1443. (d) Brettle, R.; Mosedale, A. J.
J. Chem. Soc., Perkin Trans. 1 1988, 2185.
a Conditions: [Ru]-III catalyst (5 mol %), 2 (1 equiv), 1 (1.5 equiv),
CH2Cl2 0.2 M, 16 h then nucleophile, quench additive 1 h. b Yields of
isolated products. c 1.6 equiv of amine. d 6 equiv of amine. e 3 equiv of
alcohol 0 °C. f Reaction performed in toluene followed by addition of dry
MeCN (0.2 M), 3 equiv of NaN3 (3 equiv), 2 h stirring. NMM )
N-methylmorpholine. TBS ) tert-butyldimethylsilyl.
5448
Org. Lett., Vol. 11, No. 23, 2009