O rP gl ea na si ce &d Bo i on mo to al e dc juu l sa tr mC ha er mg i ins ts ry
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COMMUNICATION
Journal Name
+
any of the phosphine adducts H to L [(M+H) expected for the
intermediates H to L: 493.3235].
Notes and references
DOI: 10.1039/C8OB03106A
1
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2, 1035; (b) J.-C. Wang, S.-S. Ng, and M. J. Krische, J. Am.
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Fig. 3 (M+H) ion peak of any of the phosphine adducts H-L.
Further, it has to be noted that the product formation can
be observed even when sub-stoichiometric quantities of
phosphine is employed (see Table 1), the rate of the reaction is
significantly improved with an increase in the amount of PBu
3
.
1
33, 4672; (g) X.-N. Zhang and M. Shi, ACS Catal., 2013, 3,
07; (h) C. T. Mbofana and S. J. Miller, ACS Catal. 2014, 4,
Thus, the observation made in Scheme 4 does not necessarily
5
1
7
reflect stoichiometric nature of the reaction.
3671; (i) S. Y. Lee, Y. Fujiwara, A. Nishiguchi, M. Kalek and G.
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To ascertain the practicality of the method phosphine-
promoted aldol reaction, a scale up reaction of 4a was
undertaken (Scheme 6). The reaction resulted in the formation
of 5a in 87% yield indicating that the reaction is scalable.
3
(
1
2
b) J. L. Methot, W. R. Roush Adv. Synth. Catal., 2004, 346,
035; (c) L.-W. Ye, J. Zhou and Y. Tang, Chem. Soc. Rev.,
008, 37, 1140; (d) B. J. Cowen and S. J. Miller, Chem. Soc.
O
O
Rev., 2009, 38, 3102; (e) S.-X.iWang, X. Han, F. Zhong, Y.
Wang and Y. Lu, Synlett, 2011, 2766; (f) S. Xu and Z. He, RSC
Adv., 2013, 3, 16885; (g) Y. C. Fan and O. Kwon, Chem.
Commun., 2013, 49, 11588; (h) Z. Wang, X. Xub and O. Kwon,
Chem. Soc. Rev., 2014, 43, 2927; (i) H. Ni, W.-L. Chan and Y.
Lu, Chem. Rev., 2018, 118, 9344; (j) H. Guo, Y. C. Fan, Z. Sun,
Y. Wu and O. Kwon, Chem. Rev., 2018, 118, 10049.
O
PBu3 (1.2 equiv)
Ph
DMF, H2O (30 equiv)
rt, 32 h
HO
Ph
4a (478 mg, 1.7 mmol)
5a (417 mg, 87%)
Scheme 6 Scale up reaction.
4
5
6
7
(a) D. Basavaiah, A. J. Rao and T. Satyanarayana, Chem. Rev.,
2
003, 103, 811; (b) Y. Wei and M. Shi, Chem. Rev., 2013, 113,
Conclusion
6659.
(a) C. E. Aroyan, A. Dermenci and S. J. Miller, Tetrahedron,
We have presented an unusual cyclopentannuative aldol
2
009, 65, 4069; (b) K. C. Bharadwaj, RSC Adv., 2015, 5,
1
8
reaction promoted by phosphine and water. This method
offers a convenient approach for the synthesis of a variety of
75923.
(a) K. C. K. Swamy, N. N. B. Kumar, E. Balaraman and K. V. P.
P. Kumar, Chem. Rev., 2009, 109, 2551; (b) S. Fletcher, Org.
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3
-hydroxy-3-dienyl-cyclopentanones fused to arenes and
1
9
heteroarenes. Even annulated cyclopentanones possessing
two contiguous stereogenic centres could be assembled in a
diastereoselective manner. However, several of our efforts to
develop an enantioselective variant of this reaction remained
unsuccessful, primarily due to the stoichiometric nature of the
reagent system. Otherwise, the methodology described herein
has demonstrated great potential and will stimulate further
research in the synthesis of new molecular architectures. We
are currently involved in extending this strategy towards the
total synthesis of complex natural products and the results will
be communicated in due course.
(a) B. M. Trost and U. Kazmaier, J. Am. Chem. Soc., 1992, 114,
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8
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2
2, 18316; (e) J. Grover, M. Raghu, R. Hazra, A. Mondal and
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9
1
(a) N. S. Dange, B.-C. Hong, C.-C. Lee and G.-H. Lee, Org.
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Conflicts of interest
The authors declare no conflict of interests.
0 B. Satpathi, L. Dutta and S. S. V. Ramasastry, Org. Lett., 2019,
2
1, 170.
Acknowledgements
This work was supported financially by IISER Mohali. We thank the
NMR, mass and departmental X-ray facilities at IISER Mohali. B.S.
thanks UGC and L.D. thanks IISER Mohali for research fellowships.
11 See the ESI for the synthesis of 4a and its analogues.
1
2 For the synthesis of structures similar to 5, see: T. Chanda, S.
Chowdhury, N. Anand, S. Koley, A. Gupta and M. S. Singh,
Tetrahedron Lett., 2015, 56, 981.
13 X-ray crystallographic data of 5m (CCDC 1865325) is
†
provided in the ESI.
1
4 See the ESI for more details.
4
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