Novel Diketopiperazine and Ten-membered Macrolides from the Entomogenous Fungus Paecilomyces tenuipes†

doi:10.7503/cjcu20140080

Abstract

Abstract:

Paecilomyces tenuipes with high edible and medicinal value was the anamorph of Cordyceps takaomontana. Four compounds were isolated from the cultured broth of Paecilomyces tenuipes by repeated column chromatography over RP-18, sephadex LH-20 and silica gel. Their structures were determined on the basis of NMR data, HRMS-EI technique and X-ray single crystal diffraction. One novel diketopiperazine (3S)-6-benzyl-3-isopropyl-1-methylpiperazine-2,5-dione(1) and one novel ten-membered macrolide(4S,10R)-4-hydroxy-10-methyloxecane-2,8-dione(2), together with two known ten-membered macrolides Cepharosporolide C(3) and Cepharosporolide E(4) were obtained. Compound 1 showed the moderate cytoto-xicity in the MTT assay against prostate cancer cells 22RV1 and DU-145 with inhibition rate of 37.8% and 38.6%, and those of compound 2 were 32.5% and 40.6%, respectively.

Key words: Paecilomyces tenuipes, (3S)-6-Benzyl-3-isopropyl-1-methylpiperazine-2, 5-dione, (4S, 10R)-4-Hydroxy-10-methyloxecane-2, 8-dione, Cytotoxicity

CLC Number:

O629.9

TrendMD:

ZHENG Yongbiao, PANG Haiyue, WANG Jifeng, CHEN Danxia, SHI Guowei, HUANG Jianzhong. Novel Diketopiperazine and Ten-membered Macrolides from the Entomogenous Fungus Paecilomyces tenuipes^†[J]. Chem. J. Chinese Universities, 2014, 35(8): 1665.

Figures/Tables 4

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Compd.	¹H NMR, δ	¹³C NMR, δ
1^a	4.42(t, 1H, J=4.0 Hz, 2-H), 3.29(dd, 1H, J=11.9, 4.0 Hz, 3a-H), 3.21(dd, 1H, J=11.9, 4.0 Hz, 3b-H), 7.13(o, 2H, 5/9-H), 7.33(o, 3H, 6/7/8-H), 2.99(d, 1H, J=1.9 Hz, 2'-H), 2.27—2.32(m, 1H, 3'-H), 0.84(d, 3H, J=7.1 Hz, 4'-H), 0.76(d, 3H, J=6.8 Hz, 5'-H), 3.02(s, 3H, 1″-H)	167.4(s, C1), 62.9(d, C2), 37.5(t, C3), 134.2(s, C4), 129.9(d, C5/9), 128.3(d, C6/8),129.3(d, C7), 165.6(s, C1'), 81.4(d, C2'), 29.8(d, C3'), 18.7(q, C4'), 15.2(q, C5'), 32.9(q, C1″)
2^b	2.83(o, 1H, 2α-H), 2.34(o, 1H, 2β-H), 4.51(o, 1H, 3-H), 2.96—2.99(m, 1H, 4α-H), 2.30(o, 1H, 4β-H), 2.01—2.07(m, 1H, 5α-H), 1.61—1.65(o, 1H, 5β-H), 2.88(o, 1H, 6α-H), 2.38(o, 1H, 6β-H), 1.68—1.70(m, 1H, 8α-H), 1.57(m, 1H, 8β-H), 4.57(o, 1H, 9-H),1.18(d, 3H, J=6.2 Hz, 10-H)	170.5(s, C1), 44.0(t, C2), 65.6(d,C3), 53.7(t, C4), 20.9(t, C5), 42.9(t, C6), 210.5(s, C7), 36.1(t, C8), 75.4(d, C9), 21.1(q, C10)
3^b	2.77(dd, 1H, J=3.2, 17.3 Hz, 2α-H), 2.33(o, 1H, 2β-H), 4.00—4.04(m, 1H, 3-H), 3.51—3.54(m, 1H, 4-H), 2.71(dd, 1H, J=2.6, 17.8 Hz, 5α-H), 2.87(dd, 1H, J=6.4, 17.8 Hz, 5β-H), 2.33—2.40(m, 2H, 7α/β-H), 2.00—2.08(m, 2H, 8α/β-H), 5.03—5.04(m, 1H, 9-H), 1.25(d, 3H, J=6.4 Hz, 10-H)	171.0(s, C1), 41.4(t, C2), 69.8(d, C3), 74.4(d, C4), 46.1(t, C5), 214.0(s, C6), 41.1(t, C7), 34.3(t, C8), 73.5(d, C9), 19.7(q, C10)
4^b	2.21(dd, 1H, J=14.4, 5.7 Hz, 2α-H), 2.35(d, 1H, J=14.4 Hz, 2β-H), 5.23(t, 1H, J=5.7 Hz, 3-H), 4.91(t, 1H, J=6.6 Hz, 4-H), 2.87(dd, 1H, J=6.6, 14.3 Hz, 5α-H), 2.53(d, 1H, J=14.3 Hz, 5β-H), 2.08(o, 1H, 7α-H), 2.11(o, 1H, 7β-H), 1.41—1.46(m, 1H, 8α-H), 2.11(o, 1H, 8β-H), 4.15—4.18(m, 1H, 9-H), 1.17(d, 3H, J=6.2 Hz, 10-H)	179.0(s, C1), 42.4(t, C2), 85.7(d, C3), 79.1(d, C4), 38.6(t, C5), 116.6(s, C6), 35.1(t, C7), 32.3(t, C8), 76.3(d, C9), 21.2(q, C10)

Compd.	¹H NMR, δ	¹³C NMR, δ
1^a	4.42(t, 1H, J=4.0 Hz, 2-H), 3.29(dd, 1H, J=11.9, 4.0 Hz, 3a-H), 3.21(dd, 1H, J=11.9, 4.0 Hz, 3b-H), 7.13(o, 2H, 5/9-H), 7.33(o, 3H, 6/7/8-H), 2.99(d, 1H, J=1.9 Hz, 2'-H), 2.27—2.32(m, 1H, 3'-H), 0.84(d, 3H, J=7.1 Hz, 4'-H), 0.76(d, 3H, J=6.8 Hz, 5'-H), 3.02(s, 3H, 1″-H)	167.4(s, C1), 62.9(d, C2), 37.5(t, C3), 134.2(s, C4), 129.9(d, C5/9), 128.3(d, C6/8),129.3(d, C7), 165.6(s, C1'), 81.4(d, C2'), 29.8(d, C3'), 18.7(q, C4'), 15.2(q, C5'), 32.9(q, C1″)
2^b	2.83(o, 1H, 2α-H), 2.34(o, 1H, 2β-H), 4.51(o, 1H, 3-H), 2.96—2.99(m, 1H, 4α-H), 2.30(o, 1H, 4β-H), 2.01—2.07(m, 1H, 5α-H), 1.61—1.65(o, 1H, 5β-H), 2.88(o, 1H, 6α-H), 2.38(o, 1H, 6β-H), 1.68—1.70(m, 1H, 8α-H), 1.57(m, 1H, 8β-H), 4.57(o, 1H, 9-H),1.18(d, 3H, J=6.2 Hz, 10-H)	170.5(s, C1), 44.0(t, C2), 65.6(d,C3), 53.7(t, C4), 20.9(t, C5), 42.9(t, C6), 210.5(s, C7), 36.1(t, C8), 75.4(d, C9), 21.1(q, C10)
3^b	2.77(dd, 1H, J=3.2, 17.3 Hz, 2α-H), 2.33(o, 1H, 2β-H), 4.00—4.04(m, 1H, 3-H), 3.51—3.54(m, 1H, 4-H), 2.71(dd, 1H, J=2.6, 17.8 Hz, 5α-H), 2.87(dd, 1H, J=6.4, 17.8 Hz, 5β-H), 2.33—2.40(m, 2H, 7α/β-H), 2.00—2.08(m, 2H, 8α/β-H), 5.03—5.04(m, 1H, 9-H), 1.25(d, 3H, J=6.4 Hz, 10-H)	171.0(s, C1), 41.4(t, C2), 69.8(d, C3), 74.4(d, C4), 46.1(t, C5), 214.0(s, C6), 41.1(t, C7), 34.3(t, C8), 73.5(d, C9), 19.7(q, C10)
4^b	2.21(dd, 1H, J=14.4, 5.7 Hz, 2α-H), 2.35(d, 1H, J=14.4 Hz, 2β-H), 5.23(t, 1H, J=5.7 Hz, 3-H), 4.91(t, 1H, J=6.6 Hz, 4-H), 2.87(dd, 1H, J=6.6, 14.3 Hz, 5α-H), 2.53(d, 1H, J=14.3 Hz, 5β-H), 2.08(o, 1H, 7α-H), 2.11(o, 1H, 7β-H), 1.41—1.46(m, 1H, 8α-H), 2.11(o, 1H, 8β-H), 4.15—4.18(m, 1H, 9-H), 1.17(d, 3H, J=6.2 Hz, 10-H)	179.0(s, C1), 42.4(t, C2), 85.7(d, C3), 79.1(d, C4), 38.6(t, C5), 116.6(s, C6), 35.1(t, C7), 32.3(t, C8), 76.3(d, C9), 21.2(q, C10)