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Ketone-imide versus ketone-oxime reductive cross-coupling promoted by samarium diiodide: new mechanistic insight gained from a failed aminocyclopentitol synthesis.

[reaction: see text] The intramolecular 1,6-ketone/imide reductive coupling promoted by samarium diiodide competes favorably with an alternative 1,5-ketone/oxime ether coupling in a keto-oxime substrate derived from D-glucosamine N-protected with a phthalimido group. This pinacol coupling reaction affords new homochiral alpha-hydroxylactam scaffolds that could be useful in diversity-oriented synthesis. A mechanistic proposal for this reaction that explains the experimental results is supported by DFT quantum-mechanical calculations on model compounds.

Cyclization↗

An unusual samarium diiodide mediated reductive ring contraction of a tricyclic oxazine to a highly-functionalized cyclopentane and cyclobutane.

[reaction--see text] Samarium diiodide mediated reductive ring contraction of a substituted tricyclo[2.2.2]oxazine at 25 degrees C leads to a mixture of cyclopentane and cyclobutane rearrangement products with complete diastereoselectivity in each case. At -78 degrees C, the anticipated amidocyclohexanol reduction product is obtained exclusively, while the cyclopentane is the sole product at reflux in THF.

Cyclobutanes↗

A glycosylation protocol based on activation of glycosyl 2-pyridyl sulfones with samarium triflate.

[reaction--see text] Reaction of glycosyl 2-pridyl sulfones (e.g.,2) with alcohols and samarium(III) triflate affords glycosides in moderate to excellent yields. Benzylated sulfones can be activated in preference to their benzoylated counterparts, and the methodology has been used to prepare di- and trisaccharides containing both furanose and pyranose residues. Thioglycosides do not react under these conditions, and the sulfones are inert to the N-iodosuccinimide/silver triflate promoter system commonly used to activate thioglycosides. This selectivity allowed the efficient preparation of oligosaccharides via orthogonal glycosylation protocols.

Alcohols↗

Samarium(II)-mediated 4-exo-trig cyclization. A stereocontrolled approach to the core of pestalotiopsin A.

[reaction: see text] Pestalotiopsin A is a structurally unique caryophyllene-type sesquiterpene which has shown immunosuppressive activity and cytotoxicity in preliminary assays. A stereocontrolled approach to the functionalized 2-oxabicyclo[3.2.0]heptane core of pestalotiopsin A is described. The approach includes a samarium(II)-mediated 4-exo-trig cyclization and a trans-lactonization process triggered by the addition of alkylytterbium reagents to a cyclobutanone intermediate.

Cyclization↗

Samarium(II) iodide mediated radical/polar crossover reactions of cyclobutenes. An efficient approach to the BCD ring system of the penitrems.

[reaction: see text] Radical/polar crossover reactions of derivatives of 1-(2-cyclobutenyl)-2-(2-iodoaryl)ethanones with acetone promoted by samarium diiodide and HMPA provide 1-(1-hydroxy-1-methylethyl)-2,2a,4,8b-tetrahydro-1H-cyclobuta[a]naphthalen-3-one derivatives in about 50% isolated yield. This reaction shows promise for construction of the BCD ring fragment of the penitrems.

Alkaloids↗

Dual-isotope imaging of neutron-activated erbium-171 and samarium-153 and the in vivo evaluation of a dual-labeled bilayer tablet by gamma scintigraphy.

The feasibility of dual-label scintigraphic studies which use the neutron-activated isotopes erbium-171 and samarium-153 is described. Experimental details are provided to correct and minimize the compton scatter contribution of 171Er into the lower-energy 153Sm window. The results from this study demonstrate that this dual-label procedure is sensitive enough to monitor simultaneously the behavior of two discrete regions of the same unit dose in the gastrointestinal tract of man.

Digestive System↗

Asymmetric conjugate reductions with samarium diiodide: asymmetric synthesis of (2S,3R)- and (2S,3S)-[2-2H,3-2H]-leucine-(S)-phenylalanine dipeptides and (2S,3R)-[2-(2)H,3-2H]-phenylalanine methyl ester.

The highly diastereoselective samarium diiodide and D(2)O-promoted conjugate reduction of homochiral (E)- and (Z)-benzylidene and isobutylidene diketopiperazines (E)-5,7 and (Z)-6,8 has been demonstrated. This methodology allows the asymmetric synthesis of methyl (2S,3R)-dideuteriophenylalanine 27 in > or = 95% de and >98% ee, and (2S,3R)- or (2S,3S)-dideuterioleucine-(S)-phenylalanine dipeptides 37 and 38 in moderate de, 66% and 74% respectively. A mechanism is proposed to account for this process.

Crystallography, X-Ray↗

Creating carbon-carbon bonds with samarium diiodide for the synthesis of modified amino acids and peptides.

In this perspective, an overview of our experiences on the application of samarium diiodide in organic synthesis for the preparation of amino acid and peptide analogues is presented. Three different carbon-carbon bond forming reactions are discussed, including side chain introductions, gamma-amino acid synthesis and acyl-like radical additions for the construction of C-C mimics of the peptidic bonds.

Alkylation↗

Force generation by orthodontic samarium-cobalt magnets.

The use of samarium-cobalt (Sm-Co) magnets for light force application is a relatively new concept in orthodontic tooth movement. This study reports on the forces generated by these magnets. Magnets were attached to aluminum rods mounted in a universal testing machine. The magnets were initially separated by 10 mm were moved toward each other at 2.5mm/min in repulsion or attraction, depending upon the magnetic pole orientation. The magnets were also positioned initially in contact and then moved apart at a rate of 2.5mm/min, again producing repulsion or attraction, depending upon the pole orientation. The Sm-Co magnets exhibit very large forces when in close approximation but forces decrease markedly at separations greater than 2mm. The force, P, generated between magnets is determined by their separation, d, and follows the relationship P = dn. At magnet separations of 0 to 2mm, the exponent n is equal to -0.4; at separations of 2mm to 7mm, exponent n equals -2.1 for both attraction and repulsion. Thus the classic Coulomb law of magnetic force was followed only at magnet separations of greater than 2mm. Force-separation behavior and the high cost of these magnets may not justify their routine clinical use.

Cobalt↗

Evaluation of samarium-153 for synovectomy in an osteochondral fragment-induced model of synovitis in horses.

OBJECTIVE: To determine the effects of intraarticular administration of Samarium-153 (153Sm) bound to hydroxyapatite microspheres (153SmM) on an osteochondral chip-induced synovitis. STUDY DESIGN: Sixty days after implantation of autogenous osteochondral fragments in the middle carpal and metacarpophalangeal joints, 153SmM was administered into 1 joint of each type. The contralateral joints were used as untreated controls. ANIMALS OR SAMPLE POPULATION: Fifteen horses without preexisting joint disease were randomly divided into 2 groups (7 in the carpal group, 8 in the metacarpophalangeal group). METHODS: Horses had osteochondral fragments that were harvested from the lateral ridge of the trochlea of the talus and implanted bilaterally into a middle carpal joint and a metacarpophalangeal joint; the opposite joint type served as a control. Sixty days later, 10 to 15 mCi of 153SmM (20 to 50 microm diam) was injected into the fragment-implanted joints. Three horses were treated with nonradioactive hydroxyapatite fragments. Horses were examined clinically until they were killed 14 or 30 days later. Control and treated joints were examined grossly and microscopically to determine the effects of 153SmM on synovial membrane and cartilage. RESULTS: Intraarticular 153SmM caused a transient flare with lameness, effusion, and edema for 48 to 72 hours. Implanted osteochondral chips induced a synovitis characterized by variable degrees of joint damage and synovial infiltrate. Use of 153SmM resulted in synovectomy of variable depth and extent. CONCLUSIONS: Intraarticular 153SmM may be a useful method for synovectomy of inflamed synovial membrane. CLINICAL RELEVANCE: With further testing, radioactive pharmaceuticals might become useful clinical treatments for persistent synovitis not responsive to conventional techniques.

Analysis of Variance↗

Samarium-153-EDTMP in the treatment of refractory rheumatoid arthritis.

We examined the preliminary safety and efficacy of intravenous samarium-153-EDTMP (Sm-153) in the treatment of refractory rheumatoid arthritis (RA). In an open-label sequential group comparison of 0.5, 1.0, and 2.0 mCi/kg, Sm-153 was administered as a single intravenous infusion to 24 patients with refractory disease. Across treatment doses, the frequency of American College of Rheumatology (ACR) 20% responses was 25%, 29%, 25%, and 33% at 2, 4, 8, and 12 weeks, respectively. Expected significant declines in absolute neutrophil count, hemoglobin, and platelet counts were observed with nadirs seen between 2-4 weeks. Sm-153, at doses of 0.5 and 1.0 mCi/kg, is well tolerated but minimally effective in the treatment of refractory RA as measured using ACR response criteria.

Adolescent↗

Radiopharmaceutical therapy of 5T33 murine myeloma by sequential treatment with samarium-153 ethylenediaminetetramethylene phosphonate, melphalan, and bone marrow transplantation.

BACKGROUND: Total-body irradiation, followed by hematopoietic system rescue by bone marrow transplantation (BMT), has been found to improve the response of patients with multiple myeloma to treatment with melphalan. The problems of nonhematopoietic toxicity from whole-body irradiation might be circumvented by using a bone-seeking radiopharmaceutical, such as samarium-153 ethylenediaminetetramethylene phosphonate (153Sm-EDTMP), to ablate the bone marrow. PURPOSE: A mouse model system for multiple myeloma was used to evaluate the potential therapeutic efficacy of sequential therapy with 153Sm-EDTMP, melphalan, and BMT. METHODS: Female C57BL/KaLwRij mice were inoculated with 8 x 10(5) 5T33 murine myeloma cells. Treatment protocols were begun 3 or 10 days later, when the myeloma was either confined to bone marrow or disseminated in liver, spleen, and lymph nodes, simulating human multiple myeloma. 153Sm, a potent beta particle-emitting radioisotope of short half-life (46.7 hours), was linked to the bone-seeking chelate EDTMP. Animals in the first treatment group were each given 22.5 MBq 153Sm-EDTMP via the jugular vein (day 3 or 10), followed by 18.5 mg/kg melphalan (maximum tolerated dose) given intraperitoneally 5 days later (day 8 or 15) and syngeneic BMT another 2 days later (day 10 or 17). Survival in groups of six to 10 animals for each time series was compared with that in mice left untreated (control cohort), in mice treated with 153Sm-EDTMP alone (day 3 or 10), or in mice treated with melphalan alone (day 8 or 15). The hematopoietic systems of animals in the latter two treatment groups recovered full function, obviating the necessity of BMT. The end point was onset of paraparesis, at which time the animals were immediately killed by carbon dioxide asphyxiation. RESULTS: Median survival in untreated control animals was 23 days in those with localized disease and 24 days in those with disseminated myeloma. Treatment with 153Sm-EDTMP alone improved survival to a median of 29 days when commenced on day 3 and 30 days when begun on day 10. Melphalan treatment alone improved the median survival to 31 days for animals with localized myeloma and 34 days in animals with disseminated disease. Additional improvement in survival to a median of 42 days was achieved in animals treated 3 days after tumor inoculation with sequential 153Sm-EDTMP, melphalan, and BMT; median survival was 40 days using this regimen in animals with disseminated myeloma. CONCLUSIONS: Animals in all three treatment protocols survived longer than those left untreated after inoculation with myeloma cells (P < .001). Sequential treatment with 153Sm-EDTMP, melphalan, and BMT was significantly more effective than single-agent treatment (P < .01). No evidence of radiotoxicity was detected in nonhematopoietic organs. IMPLICATIONS: The survival advantage conferred by our sequential treatment protocol suggests its potential clinical usefulness in the treatment of multiple myeloma and other hematologic malignancies in humans.

Animals↗

The first synthesis of herbicidin B, a tricyclic-sugar adenine nucleoside antibiotic, using samarium diiodide-promoted aldol-type C-glycosidation reaction as a key-step.

A first total synthesis of the nucleoside antibiotic herbicidin B (1) was achieved in which a novel aldol-type C-glycosidation reaction promoted by samarium diiodide (SmI2) was used as a key step. Construction of the desired stereochemistry of the tricyclic-sugar moiety was successfully achieved by conformational restriction strategy based on repulsion between adjacent bulky protecting groups on the pyranose ring.

Anti-Bacterial Agents↗

Changes in articular synovial lining volume measured by magnetic resonance in a randomized, double-blind, controlled trial of intra-articular samarium-153 particulate hydroxyapatite for chronic knee synovitis.

OBJECTIVE: Magnetic resonance techniques have recently been investigated as tools with which to monitor inflammatory joint disease. Our aim was to use a contrast-enhanced T1-weighted protocol to monitor the short-term changes in knee synovial lining volume in a double-blind, randomized, controlled trial of intra-articular samarium-153 particulate hydroxyapatite (Sm-153 PHYP). METHODS: Twenty-four out-patients with chronic knee synovitis, from a cohort who had been recruited to a long-term clinical efficacy trial, were recruited for this study. Patients received either intra-articular Sm-153 PHYP combined with 40 mg triamcinolone hexacetonide or 40 mg intra-articular triamcinolone hexacetonide alone. Synovial lining volumes were calculated from three-dimensional T1-weighted contrast-enhanced images made before and after contrast enhancement with thresholding and pixel counting, immediately before and 3 months after treatment. RESULTS: Paired pre- and post-treatment magnetic resonance data were obtained for 18/24 (75%) patients. There was no significant difference in mean pre-treatment synovial volume between the two treatment groups (139 vs 127 ml). A mean reduction in synovial lining volume was detected in the Sm-153 PHYP/steroid-treated group (139 to 110 ml, P = 0.07) and in the steroid-treated group (127 to 58 ml, P < 0.001). The reduction was significantly greater in the steroid-treated group (-61% vs -23%, P < 0.05). CONCLUSIONS: Short-term changes in articular synovial lining in response to intra-articular treatment for chronic synovitis may be monitored by magnetic resonance imaging. After 3 months, a greater mean reduction in synovial lining volume had occurred in response to intra-articular steroid alone compared to combined Sm-153 PHYP/steroid injection.

Adult↗

Chromosomal analysis of peripheral lymphocytes of patients before and after radiation synovectomy with samarium-153 particulate hydroxyapatite.

OBJECTIVE: Radiation synovectomy may be indicated for the treatment of chronic synovitis. A number of factors may affect its current use, including availability, limited evidence for its efficacy compared to intra-articular glucocorticoid, and concerns regarding the potential long-term effects of radiation exposure, particularly in younger patients. Specific chromosome-type abnormalities in peripheral lymphocytes can be useful indicators of whole-body radiation exposure. The frequency of these aberrations has been shown to increase in patients who have had radiation synovectomy using yttrium-90 by up to five times compared to baseline levels. Samarium-153 particulate hydroxyapatite (Sm-153 PHYP) is a new radiopharmaceutical currently on trial which appears to have less extra-articular leakage than yttrium-90 compounds. The aim of this study was to identify any increase in specific chromosome-type abnormalities, using published criteria, in patients following Sm-153 PHYP synovectomy of the knee. The 10 patients (five men, five women) in whom the analyses were performed had a mean age of 47 yr (range 28-70 yr). RESULTS: There was no increase in scored chromosome-type abnormalities after Sm-153 PHYP synovectomy. CONCLUSION: This study further supports the relative safety of Sm-153 PHYP compared to other radiopharmaceuticals.

Adult↗

Thermoluminescence of terbium sensitised by samarium in CaF2.

Thermoluminescence (TL) in sintered CaF2 doped with Tb4O7 has been studied for UV and X-ray irradiation. Three TL glow peaks for the Tb4O7 doped sample appeared in the temperature regions of about (1) 347-353 K, (2) 378-383 K and (3) 453-458 K, when heated at a rate of 20 K min(-1) after UV or X-ray irradiation at room temperature. It has been found that the 378 K peak intensity of the samples co-doped with Tb4O7 and Sm2O3 became stronger when compared with those doped with only terbium or samarium ions, and the TL peaks of (1) 347-353 K and (3) 453-458 K were not observed. The intensity of the 378 K peak of the co-doped sample was 12.9 times that of the sample doped only with Tb4O7. From the TL spectra and the excitation and emission spectra of photoluminescence for the CaF2 doped activators, it is concluded that the TL of Tb3+ ions is sensitised by the existence of Sm3+ ions. The 378 K TL peak may also be suitable for UV radiation dosimetry.

Calcium Fluoride↗