Phosphine-Catalyzed Annulations between Modified Allylic Derivatives and Polar Dienes
Zhang, C.; Xu, Z. Acc. Chem. Res. 2001, 34, 535; (c) Methot, J. L.;
Scheme 2 A plausible mechanism for the phosphine-catalyzed
[4+1]/[3+2] annulations between allylic derivatives 1 and polar
dienes 2
Roush, W. R. Adv. Synth. Catal. 2004, 346, 1035; (d) Ye, L.-W.;
Zhou, J.; Tang, Y. Chem. Soc. Rev. 2008, 37, 1140; (e) Cowen, B. J.;
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2012, 48, 1724.
t-BuOH
PR'3
γ
OBoc
CO2Et
CO2Et
R
R
PR'3
NC
[4] For selected examples of allenes, see: (a) Xiao, H.; Chai, Z.; Zheng,
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1
A
CN
R1
R2
2
1,4-addn.
1,2-addn.
R1, R2 = aryl
R = R1 = H
NC
CN
R2
NC
NC
CO2Et
R2
R1
PR'3
R
CO2Et
B
PR'3
[4 + 1]
R = H
[3 + 2]
C
[3 + 2]
CO2Et
PR'3
R = Me, Ph
R1
PR'3
R2
NC
CN
NC
R1
CO2Et
CN
NC
CO2Et
CN
R2
R
R2
3
4
5
reactions between allylic derivatives and 1,1-dicyano-
1,3-dienes have been preliminarily investigated. As a
result, a simple PPh3-catalyzed [4+1] annulation be-
tween allylic derivatives and 1,1-dicyano-2,4-diaryl-
1,3-dienes has been realized, which provides a facile
access to polysubstituted cyclopentenes. It is also un-
veiled that the substituents of both allylic derivatives
and 1,3-dienes impose a significant influence on the
annulation mode. In addition to the [4+1] annulation,
the regioselective [3+2] annulation reactions of the
dienes acting as a C2 unit can be readily achieved by
choosing differently substituted substrates. These dif-
ferent annulation modes provide effective synthetic
routes to the polysubstituted cyclopentenes with struc-
tural diversity. Future efforts in our laboratory will be
directed toward further expanding the substrate scope of
these annulation reactions.
[8] (a) Ref. 4r and 7c; (b) Zhou, R.; Wang, J.; Duan, C.; He, Z. Org. Lett.
2012, 14, 6134; (c) Xu, S.; Chen, R.; Qin, Z.; Wu, G.; He, Z. Org.
Lett. 2012, 14, 996; (d) Chen, R.; Xu, S.; Wang, L.; Tang, Y.; He, Z.
Chem. Commun. 2013, 49, 3543.
[9] Selected crystal data for 3a (CCDC 931716): empirical formula:
C24H20N2O2. Formula weight: 368.42. Crystal space group: triclinic,
P-1. Unit cell dimensions: a=8.369(6) Å, b=11.546(9) Å, c=
20.904(15) Å, α=103.944(17)°, β=90.962(19)°, γ=93.488(9)°.
Acknowledgement
Financial support from National Natural Science
Foundation of China (Nos. 21072100; 21121002;
21272119) is gratefully acknowledged.
F
000=776, Z=4, Dcalcd=1.251 g•cm−3, U=1956(2) Å3, T=113(2)
K, λ(Mo-Kα)=0.7107 Å. 9214 reflections collected in the range of
1.00≤θ≤27.94°, Rint =0.0443. Refinement method: full-matrix
least-squares on F2 to R1=0.0490, wR2=0.1030. The supplementary
crystallographic data for this compound can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
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