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H. Xu, J.-L. Zhang / Bioorg. Med. Chem. Lett. 21 (2011) 5177–5180
and 40%, respectively, while the final mortality rate of 9c was
56%. The afore-mentioned results will prompt us to further inves-
tigate other benzenesulfonyloxy groups with different length of
the side chain on the benzyloxy moiety of 3 as an insecticidal agent
in future.
In conclusion, 14 novel 4a-arylsulfonyloxybenzyloxy-2b-chlo-
ropodophyllotoxins (9a–g and 9a0–g0) were stereoselectively semi-
synthesized and preliminarily evaluated their activity against the
pre-third-instar larvae of M. separata in vivo at 1 mg/mL. Especially
compounds 9c0 and 9g0 exhibited the most promising and pro-
nounced insecticidal activity. In general, it preliminarily suggested
that arylsulfonyloxy groups at the C-2 position of benzyloxy moi-
ety and the length of the side chain on the benzenesulfonyloxy
group of 4a-arylsulfonyloxybenzyloxy-2b-chloropodophyllotoxins
might be important for the insecticidal activity.
Figure 5. The representative malformed pupae pictures of 9a (zjl-59), 9b (zjl-62),
9f (zjl-69), 9a0(zjl-87), 9f0(zjl-96), and 9g0 (zjl-107) during the pupation period.
Acknowledgments
This work was financially supported by National Natural
Science Foundation of China (No. 31071737), the Program for
New Century Excellent University Talents, State Education
Ministry of China (NCET-06-0868), the Fok Ying Tong Education
Foundation for Young Talents (No. 121032), and the Special Funds
of Central Colleges Basic Scientific Research Operating Expenses
(QN2009045).
Supplementary data
Supplementary data associated with this article can be found, in
References and notes
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17. Crystallographic data (excluding structure factors) for the structure of 9f0in this
paper has been deposited with the Cambridge Crystallographic Data Centre as
supplementary publication number CCDC 818540. Copies of the data can be
obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge
CB2 1EZ, UK [fax: +44 (0)1223 336033 or e-mail: deposit@ccdc.cam.ac.uk].
not be free. For example, introduction of arylsulfonyloxybenzyloxy
groups at the C-4 position of 8 via the ether bond, most of the cor-
responding compounds showed more potent insecticidal activity
than 8. Generally, introduction of arylsulfonyloxy groups at the
C-2 position of benzyloxy moiety of 3 would lead to the more po-
tent compounds than or comparable to those with the ones at the
C-4 position (except 9f and 9f0). Especially when 4-ethyl-
benzenesulfonyloxy and
3-nitro-4-chlorobenzenesulfonyloxy
groups were introduced at the C-2 position of benzyloxy moiety
of 3, respectively, the corresponding compounds 9c0 and 9g0 dis-
played more promising and pronounced insecticidal activity than
3. Interestingly, the length of the side chain (when R = H, Me, and
Et) on the benzenesulfonyloxy group of 9a–c and 9a0–c0 was
essential for the insecticidal activity. As the side chain on the ben-
zenesulfonyloxy group was lengthened, the corresponding insecti-
cidal activity was usually increased (9a vs 9b vs 9c; 9a0 vs 9b0 vs
9c0). For example, the final mortality rates of 9a and 9b were 36%