Two new (3 and 5), as well as three known (1, 2, and 4), polyynes were isolated from Devil's Club (Oplopanax horridus; Araliaceae), a medicinal plant of North America. The structures were established by 1H and 13C NMR. The absolute configurations of 2 and 5 were determined by application of Mosher's method. All the polyynes exhibited significant anti-Candida, antibacterial, and antimycobacterial activity, with an ability to kill Mycobacterium tuberculosis and isoniazid-resistant Mycobacterium avium at 10 micrograms/disk in a disk diffusion assay.

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The reaction of Li[Ph2P(NSiMe3)2] with TeCU in a 1:1 molar ratio in CH2CI2 at -78 °C, followed by warming to 23 °C, produces Pl^PCNSiMesUTeCU (1) in essentially quantitative yield. An X-ray analysis shows 1 to contain a four-membered PN2Te ring with Te-N bond distances of 2.056(3) and 2.185(3) Á. When the same reaction is carried out in a 2:1 molar ratio, the product is Ph2P(NSiMe3)2Te(Cl)NPPh2NSiMes (2), which consists of a PN2Te ring with Te-N bond distances of 2.108(3) and 2.275(4) Á and a short exocyclic tellurium-nitrogen bond of 1.922(4) Á. Crystals of 1 are monoclinic, of space group P2\!n, with a = 15.494(7) k, b = 11.580(9) Á, c = 15.823, ß = 96.46(3)°, V = 2820(2) Á3, and Z == 4. The final R and Rw values were 0.024 and 0.027, respectively. Crystals of 2 are triclinic, of space group PI, with a = 12.372(7) k,b= 17.040(6) k,c= 11.648(4) Á, a = 108.11(2)°, ß = 109.32(4), = 88.76(4)°, V = 2193(2) Á3, and Z = 2. The final R and Rw values were 0.036 and 0.037, respectively.

This investigation centers on the preparation of new binary carbon sulfides based on the 1,2-dithiole-3-thione subunit as found in the precursor dithiolate C3S5* 12'. Tricyclic CeSg, 1, was obtained in high yield by thermal elimination of H2S from the dimercaptan J8-C3S5H2. A crystallographic study confirmed a tricyclic structure of idealized D2a symmetry containing an unusual planar 1,4-dithiin unit. The crystals of 1 are monoclinic, space group P2\/c, with a = 8. 046(2), b = 9.797(3), c = 13.818(4) Á, V-1048.3(9) Á3 4, andZ = 4. The final R and Rw values were 0.036 and 0.042, respectively. The bicyclic carbon sulfide C5S7,3, was prepared from reduction of C4S6,2, with LiBEtsH, followed by addition of thiophosgene. Oxidation of CP2TÍOS-C3S5) or Zn(/3-C3S¡)22~w ith SO2CI2 afforded [¿J-C3S5],,, 4, an orange insoluble solid. Degradation of [y-CsSs], with dimethyl acetylenedicarboxylate (DMAD) afforded C3S5-2DMAD, 5, together with small amounts of C3S5 3DMAD, 6. The single-crystal X-ray structure of C3S5 -2DMAD revealed a folded 1,4-dithiin linked to a planar 1,3-dithiole. Crystals of 5 are monoclinic, space group Cc, with a = 18.760(4), b = 13.664(3), c = 7.880(2) k,V = 1957(2) Á3, and Z = 4. The least-squares refinement with anisotropic thermal parameters for all non-hydrogen atoms converged at R -0.036 and i?w = 0.047. The DMAD treatment proceeds in a similar manner with [M(/3-C3Ss)2]2~(M = Zn, Ni) to yield [M^Ss'DMADh]2-.The C3S5 DMAD ligand can subsequently be removed from the zinc complex by reaction with thiophosgene giving bicyclic C4S6 DMAD, which can also be obtained via Cp2Ti(C3Ss-DMAD).