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Spirogermanium: a new investigational drug of novel structure and lack of bone marrow toxicity.

Spirogermanium (NSC 192965) is a new metallic investigational anticancer drug of novel heterocyclic structure. Although its mode of action has not been fully elucidated, it appears that spirogermanium is not a phase or cell cycle specific drug and inhibits DNA, RNA and protein synthesis, the protein synthesis being the most susceptible to this agent. Spirogermanium has shown cytotoxic activity in vitro against several human tumor cell lines at concentrations (1 micrograms/ml) that were also found toxic to the cultured rat neurons. Although spirogermanium has no effect on normal bone marrow colony forming cells in mice, dogs, or man, it has revealed cytotoxic activity in vitro against human myeloid leukemia cell line K 562 at clinically achievable concentrations. These in vitro findings, indicating selective cytotoxic activity against leukemic cells suggest this drug as a candidate for clinical studies in acute and chronic leukemias. Spirogermanium has revealed activity in vivo against intraperitoneally implanted Walker 256 sarcoma, 13762 mammary adenocarcinoma, and 11095 prostatic carcinoma in rats, but no antitumor activity in vivo was found in the murine tumors used in the past by the NCI screen (L 1210 and P 388 leukemia, B 16 melanoma, Lewis lung carcinoma). Spirogermanium is remarkable for its lack of bone marrow toxicity confirmed in preclinical toxicology and clinical studies; moderate, predictable, and reversible CNS toxicity is dose-limiting. Activity in malignant lymphoma, ovarian cancer, breast cancer, large bowel cancer, and prostatic cancer was reported in the clinical studies. The drug is currently under clinical investigation against the wide spectrum of solid tumors and malignant lymphomas. The dose of 80-120 mg/m2, given by 60' infusion three times a week, is currently used and tolerated in Phase II clinical studies. The recently introduced five days continuous infusion schedule has been also under clinical investigation and the doses of 250-300 mg/m2/day are recommended for Phase II studies. Of interest are results reported in this paper of spirogermanium in vitro preferential activity against the resistant strains of Plasmodium falciparum at clinically achievable concentrations suggesting this drug as a possible new antimalarial agent of novel structure.

Animals↗

Phase I study of oral spirogermanium.

Thirty-three patients with advanced malignancy were treated with oral spirogermanium in a Phase I study to determine a maximum tolerated dose. Patients were entered in the study at doses of 100, 200, and 300 milligrams daily. The dose-limiting toxicity was gastrointestinal with moderate nausea and vomiting occurring with the 300 milligram dose. No myelosuppression or renal dysfunction was noted. Elevations of serum transaminase were seen in 41 percent of the patients at study entry. While abnormalities in hepatic function were recorded during the study, the relationship to spirogermanium could not be determined. No patient exhibited clinical hepatic dysfunction or elevation of serum bilirubin. It is recommended that future studies of oral spirogermanium incorporate careful monitoring of these parameters. Two patients with lymphoproliferative disorders had objective responses to therapy. A dose of 200 milligrams is recommended for further Phase II trials.

Administration, Oral↗

Phase II protocol for the evaluation of new treatments in patients with advanced gastric carcinoma: results of ECOG 5282.

The study was a Phase II randomized study to evaluate the efficacy of new agents for the treatment of advanced gastric carcinoma. Patients were randomized to receive single agent chemotherapy with mitoxantrone, etoposide, aclacinomycin-A or spirogermanium. The patients were stratified by prior use of chemotherapy, prior doxorubicin use and ECOG performance status. Patients with a history of cardiac disease or prior doxorubicin exceeding a dose of 400 mg/m2 were restrictively randomized to sopirogermanium or etoposide only. One hundred and fourteen patients were registered for the study. Among 98 evaluable patients there were only two partial responses (both in the etoposide arm), and one complete response in the mitoxantrone arm. The median survival on the study was 3.3 months. One hundred and six patients were analyzable for toxicity. There were four treatment-related deaths and four life-threatening toxicities. Because of low response rates and relatively high toxicities the studied compounds were not deemed worth further investigation for advanced gastric cancer.

Aclarubicin↗

Effects of spirogermanium on the in vitro assembly and disassembly of brain microtubules.

The inhibition of microtubule proteins (MTP) assembly by Spirogermanium (SP, 1.25-100 microM) has been studied. Assembly at 37 degrees C was monitored by turbidity measurements and electron microscopy. For SP in 1:1 protein-drug ratio the inhibition of assembly was 50%. Addition of 12.5 microM SP to microtubules induced spontaneous disassembly. SP had less effect on the assembly of pure tubulin (tubulin 6S). Complete inhibition of assembly induced by glycerol and Mg2+ was found with 250 microM and the ratio of SP to tubulin to obtain 50% inhibition was higher than with MTP.

Antineoplastic Agents↗

Trypanosoma cruzi: inhibition by spirogermanium hydrochloride.

Spirogermanium is an antineoplastic agent that has been shown to be useful for the treatment of a variety of solid tumors and Plasmodium falciparum infection. We found that this agent, at concentrations of 1-10 micrograms/ml, markedly inhibited the growth of epimastigotes of Trypanosoma cruzi. This inhibition of growth was seen in liver infusion tryptose cultures as well as on agar where colonial growth was inhibited markedly. Ultrastructural studies demonstrated that affected organisms were round and swollen and contained vacuoles, lamellar structures, and multivesicular bodies. Spirogermanium also significantly decreased the growth of intracellular amastigotes in myotubes. Pretreatment of myotubes with the agent protected them from infection with trypomastigotes but tachyzoites of Toxoplasma sp. readily infected pretreated cells. These data suggest that spirogermanium may be useful as a chemotherapeutic agent against T. cruzi.

Animals↗

Improved synthesis of a protected 11-oxoestrone.

An improved synthesis of 11-oxoestrone-3-acetate-17-ethyleneketal is reported. Adjustments are proposed for the oxidation of estrone by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone into 9(11)-dehydroestrone. A complete hydroboration-oxidation of the resulting ketal, by means of borane-methylsulfide complex, gives the corresponding 11-hydroxy derivative. This latter compound is then acetylated for successful oxidation with pyridinium chlorochromate on alumina. The overall yield is 30%.

Acetylation↗

A model to study drug effects on lymphoma and normal cell populations using the AKR/J mouse.

The existence of an AKR subline, AKR(Rb6.15)1A1d, with a chromosome marker provided a means to differentiate between proliferating lymphoma and normal cell populations within a single animal. An AKR(Rb6.15)1A1d lymphoma cell line has been maintained for 6 yr by serial passage in AKR/J recipients. The mice die in 7 +/- 2.0 days with evidence of extensive infiltration of the tissues by lymphoma cells. Cytogenetic analysis showed that approx. 1% of the metaphase cells in the bone marrow of mice at day 1 of the lymphoma passage were of the AKR(Rb6.15)1A1d donor-type. This increased to 54% by day 4 and 96% by day 6. The number of donor-type metaphase cells per humerus increased from 3.4 +/- 0.29 (X 10(3] at day 1 to 2.0 +/- 0.49 (X 10(5] at day 4 with a concomitant decrease in the number of non-lymphoma host-type metaphase cells. The population doubling time of donor-type metaphase cells per humerus was 12 +/- 1.4 h. At day 4, there was a significant decrease in the percentage of donor-type metaphase cells in mice that had been treated with BCNU (19.0 +/- 5.85%) or spirogermanium (38.6 +/- 5.85%) 24 h earlier. For BCNU treated animals, this also represented a decrease to 4.4 +/- 1.1 (X 10(4] donor-type metaphase cells per humerus.

Animals↗

Suppressor cell induction by the anticancer drug spirogermanium.

Spirogermanium is a metal-containing compound reported to have antitumor, antiarthritic, antimalarial and immunoregulatory activity. In this study we have demonstrated that spirogermanium inhibited antibody synthesis to sheep red blood cells in BDF1 mice in vivo. Spleen cells from these treated mice were unable to respond to this antigen in vitro, and suppressed both the antibody response of normal cells to SRBC and the mitogenic response of normal cells to Concanavalin A in co-culture assays. The cells responsible for this suppression did not belong to the T cell lineage since treatment with anti-Thy-1.2 antiserum and complement did not abrogate the suppression. The suppressor cells were found to be radiation resistant and nylon wool adherent. Plastic adherence or passage over Sephadex G10 partially removed the suppression indicating the contribution, at least in part, of a suppressor macrophage. The plastic non-adherent population of cells also contained suppressor cells which were detected following anti-thy-1.2 treatment and selection by panning on anti-IgG coated plates. Fluorescent antibody and flow cytometry technology showed the population of suppressor cells to be 90% immunoglobulin positive, indicative of a B cell lineage.

Animals↗

Asymmetric synthesis of novel tetrahydroquinoline derivatives with a sugar building block and their bioactivities.

Some novel spiro-tetrahydroquinolines were stereoselectively synthesized by using keto-sugar derived from sucrose as a building block in one pot under mild conditions. The in vitro immunobiological activity and cytotoxicity of these novel tetrahydroquinolines were investigated. The results implied that these spiro-compounds have obvious bioactivity and may be structurally modified to improve bioactivity further.

Antineoplastic Agents↗

Properties of silorane-based dental resins and composites containing a stress-reducing monomer.

OBJECTIVE: To evaluate properties of silorane-based resins and composites containing a stress reducing monomer. METHODS: Resin mixtures and composites were formulated containing (a) a developmental stress reducing monomer [TOSU; Midwest Research Institute]; (b) Sil-Mix (3M-ESPE); (c) photo cationic initiator system. Standard BISGMA/TEGDMA resin (B/T) and composite (Filtek Z250) were used as controls. Polymerization volume change was measured using a NIST mercury dilatometer and polymerization stress using an Enduratec mechanical testing machine. Three point bend tests determined flexural elastic modulus, work of fracture, and ultimate strength (ADA 27; ISO 4049). Fracture toughness was measured using ASTM E399-90. Four groups of resins and composites were tested: Sil-Mix, methacrylate standard, and Sil-Mix with two addition levels of TOSU. An ANOVA was used and significant differences ranked using Student-Newman-Keuls test (alpha=0.05). RESULTS: Polymerization stress values for resins containing TOSU were significantly less than the other materials. Polymerization shrinkage values for Sil-Mix formulations were significantly less than for B/T, but were not different from each other. TOSU-containing formulations generally had somewhat lower mechanical properties values than Sil-Mix or B/T. Polymerization stress values for Sil-Mix-based composites were significantly less as compared to Z250. The 1wt.% TOSU composite had the lowest stress. No difference between composite groups was noted for fracture toughness or work of fracture. For ultimate strength, the 5wt.% TOSU formulation differed significantly from Z250. All Sil-Mix formulations had elastic modulus values significantly different from Z250. SIGNIFICANCE: The ability of TOSU to reduce polymerization stress without a proportional reduction in mechanical properties provides a basis for improvement of silorane-based composites.

Alkanes↗

Synthetic studies on heterocyclic natural products.

This article reviews past and ongoing research in the author's laboratory directed toward the synthesis of natural products displaying an azaspirocyclic framework, or incorporating a medium-ring nitrogen heterocycle. New synthetic technologies were devised in order to address the synthetic problems posed by the target molecules. Thus, efforts in the area of azaspirocyclic substances have relied on an oxidative amidation of phenols promoted by iodobenzene diacetate, whereas access to medium-ring nitrogen heterocycles has been secured by means of a ring expansion sequence that relies on the fragmentation of an aziridine triggered by a homo-Brook transposition. Details of the development of these technologies are presented, together with applications to the total synthesis of FR-901483, TAN-1251C, cylindricines, and mitomycinoids.

Aza Compounds↗

Total synthesis of tricyclic azaspirane derivatives of tyrosine: FR901483 and TAN1251C.

A solution to the long-standing problem presented by the oxidative cyclization of a phenolic 3-arylpropionamide to a spirolactam has been developed in this laboratory via oxazoline chemistry. This research was motivated by our interest in some novel tricyclic azaspirane natural products formally derived from tyrosine, such as FR901483 and TAN1251C. In this paper, we disclose full details of the total synthesis of these substances.

Aza Compounds↗

Biomimetically inspired total synthesis and structure activity relationships of 1-O-methyllateriflorone. 6 pi electrocyclizations in organic synthesis.

The total synthesis of 1-O-methyllateriflorone (2) is described. The construction of the cage-like domain of the molecule involved a biomimetic Claisen/Diels-Alder cascade, whereas the novel spiroxalactone framework was generated by an intramolecular Michael reaction within precursor 16a involving the carboxylate residue as the nucleophile. This finding might bear on the biosynthetic pathway by which nature forms lateriflorone. Described herein is also an interesting cascade sequence involving facile 6 pi electrocyclizations which leads to complex benzopyran systems. The biological evaluation of a small library of lateriflorone analogues and related systems establishing the first SAR within this class of compounds is also included. Among the most active compounds against tumor cells are 2, 16b, 56, 58, and 59.

Benzopyrans↗

Synthesis and antimalarial activity of novel medium-sized 1,2,4,5-tetraoxacycloalkanes.

CsOH- or Ag(2)O-mediated cycloalkylation of (alkylidene)bisperoxides 3 and 1,n-dihaloalkanes (n = 3-8) provided the corresponding medium-sized 1,2,4,5-tetraoxacycloalkanes 4-8 in moderate yields. Subsequent evaluation of the antimalarial activity of the cyclic peroxides 4-8 in vitro and in vivo revealed that 1,2,6,7-tetraoxaspiro[7.11]nonadecane 4a has considerable potential as a new, inexpensive, and potent antimalarial drug.

Animals↗

A new photochromic 8pi-system based on an azaheptatriene-tetrahydroazepinoisoquinoline electrocyclization.

A new photochromic family of tetrahydroazepinoisoquinolines (THAI) 4a-i has been prepared. It undergoes light-induced ring opening from spiro compounds 4 to betaines 3 that decolorize in a very fast cyclizing reaction. Depending on substitution of the precursors 1 and 6, the photochromic styryltetrahydroindolizines (THI) 5k-q are formed in a periselective way. The conformation and configuration of the new photochromic THAI 4 and THI 5 were investigated by NMR and the structure of both compounds was proven by X-ray analysis. The photochromic properties were studied by laser flash photolysis, which afforded the lifetime of the colored form 3 and 3' in the micro- or nanosecond range.

Journal Article↗

Stereocontrolled preparation of a nonpeptidal (-)-spirobicyclic NK-1 receptor antagonist.

The synthesis of a spirobicyclic NK-1 receptor (Substance-P) antagonist 1 antipode is described. Retrosynthetic analysis reveals an allylic halide A bearing the cyclopropoxy-substituted aryl group and a 2-phenyl-3-piperidone B. The stereochemistry in the spirobicyclic system bearing three chiral centers is initially set via a highly diastereoselective zinc-mediated coupling of the allylic bromide 23 to the optically active ketopiperidine 3. The remaining benzylic asymmetric center is set by a diastereoselective hydroboration followed by cyclization to the spirobicyclic system.

Aza Compounds↗

Synthesis and oxidation behavior of 2,4,5,7,8-pentamethyl-4H-1,3-benzodioxin-6-ol, a multifunctional oxatocopherol-type antioxidant.

2,4,5,7,8-Pentamethyl-4H-1,3-benzodioxin-6-ol (PBD, 1) is a novel 3-oxa-tocopherol-type stabilizer, which is obtained as a mixture of two diastereomers by condensation of trimethylhydroquinone with acetaldehyde in an acid-catalyzed reaction. The oxidation behavior of 1 is governed by the amount of water available. In aqueous media, 1 is oxidized by one oxidation equivalent to 2,5-dihydroxy-3,4,6-trimethylacetophenone (3) via 2-(1-hydroxyethyl)-3,5,6-trimethylbenzo-1,4-quinone (2). The acid-catalyzed conversion of 2 into 3 proceeds in solution with first-order kinetics with regard to 2 but works also in solid phase. Oxidation in the presence of just 1 equiv of water produces acetophenone 3 as well, but according to a different mechanism involving o-quinone methide 5 and styrene derivative 6, from which finally acetaldehyde is released. A [1,5]-sigmatropic proton shift from the C-4a methyl group to the exocyclic methylene group in 5 causes formation of 6, as demonstrated by labeling experiments. In addition, the presence of both intermediates was proven by hetero-Diels-Alder trapping reactions. In the absence of water, oxidation of 1 produces chromenone 10 via the intermediates 5 and 6 and chromanone 9, and oxidation of 9 to 10 is preferred to oxidation of starting material 1. When the formation of an exocyclic methylene group at C-4 is impossible as a result of structural prerequisites, as in the diphenyl derivative 12, the initially generated o-quinone methide 5 cannot form 6 but undergoes dimerization to spiro-compounds. The transformation of p-quinone 2 into acetophenone 3 might contribute to the chemistry of tocopherols oxidized at C-4, i.e., 4-hydroxy-alpha-tocopherol and 4-oxo-alpha-tocopherol, which have been proposed as precursors of natural vitamin E metabolites.

Antioxidants↗