Access to isocarbacyclin derivatives via substrate-controlled enolate formation: total synthesis of 15-deoxy-16-(m-tolyl)- 17,18,19,20-tetranorisocarbacyclin

[reaction: see text] We describe a convergent and flexible synthesis of 15-deoxy-16-(m-tolyl)-17,18,19,20-tetranorisocarbacyclin (15-deoxy-TIC), a simple isocarbacyclin derivative. The synthesis takes advantage of two key step reactions: a regioselective deprotonation of the described ketone under substrate control which is then trapped, as the enol triflate, to generate the C6-C9alpha endocyclic double bond, followed by an sp2-sp3 Pd-catalyzed cross-coupling reaction (C5-C6) with a suitable primary alkyl Grignard reagent. Introduction of the C13-C14 (E)-double bond in the omega-side chain is performed by the Julia-Kocie?ski olefination.     

Observation of Diastereomers by 199Hg NMR

The diastereomeric parts of HgP bonded Hg[P(O)(OBuⁿ)ph]₂ give rise to different ¹⁹⁹Hg NMR patterns. No enantiomeric discrimination occurs in the synthesis. Ligand redistribution reactions prevent the separation of the diastereomers.     

Über die Mischbarkeit von UN mit LaN,CeN, PrN,NdN, SmN,GdN, DyN,und ErN

X-Ray studies of the mixed nitride phases indicate complete miscibility in all cases. Lattice parameters generally showed negative deviations from the additivity rule.

Teilauszug aus der Dissertation des Dipl.-Ing.J. Waldhart an der Technischen Universität Wien, Österreich.     

Synthesis of erythro-alpha-amino beta-hydroxy carboxylic acid esters by diastereoselective photocycloaddition of 5-methoxyoxazoles with aldehydes

A new photoaldol route to alpha-amino-beta-hydroxy carboxylic acid esters is initiated by the photocycloaddition of aromatic or aliphatic aldehydes to 5-methoxyoxazoles. The 4-unsubstituted 5-methyloxazole 1 gave the cycloadducts 8a-f in high yields and excellent exo-diastereoselectivities. Hydrolysis of 8a-f gives the N-acetyl alpha-amino-beta-hydroxy esters 9a-f, which could be subsequently converted into the corresponding Z-didehydro alpha-amino acids 10a-f. Quartenary alpha-amino-beta-hydroxy esters 12, 14, 16, 18, and 20, which are stable against dehydration, were obtained from the 4-alkylated 5-methoxyoxazoles 2-6, in most cases highly erythro-selective due to the high degree of stereocontrol (exo) at the photocycloaddition (to give 11, 13, 15, 17, and 19) level. The relative configurations of the N-acetyl alpha-amino-beta-hydroxy esters were determined by NMR spectroscopy and comparison with chiral pool-derived compounds as well as by X-ray structure determination of the ester 23, formed by hydrolysis of the cycloadduct 22, derived from photocycloaddition of propionaldehyde to the isoleucine-derived oxazole 21.     

A photochemical route for efficient cyclopeptide formation with a minimum of protection and activation chemistry

An elaborated protocol is described which allows the efficient transformation of di-, tri-, and tetrapeptides into cyclopeptides with a minimum of protection and activation chemistry using the photoinduced electron transfer initiated decarboxylation of N-phthaloyl peptides resulting in C-C coupling between the initially formed carbon radicals.     

Synthesis, Characterization, and Electrochemistry of sigma-Bonded Cobalt Corroles in High Oxidation States

The synthesis, electrochemistry, spectroscopy, and structural characterization of two high-valent phenyl sigma-bonded cobalt corroles containing a central cobalt ion in formal +IV and +V oxidation states is presented. The characterized compounds are represented as phenyl sigma-bonded cobalt corroles, (OEC)Co(C(6)H(5)) and [(OEC)Co(C(6)H(5))]ClO(4), where OEC is the trianion of 2,3,7,8,12,13,17,18-octaethylcorrole. The electronic distribution in both molecules is discussed in terms of their NMR and EPR spectroscopic data, magnetic susceptibility, and electrochemistry.     

Selective mono,bis, and trisiminoformylation of 2,4,6-trialkyl-1,3,5-triazines - unusual enol acylenamine tautomerism of hydroxyalkenyl-1,3,5-triazines

2,4,6-Trialkyl-1,3,5-triazines 1 can selectively be mono, bis or trisiminoformylated by reaction with trismorpholinomethane 2 or chloromethylene iminium salts 3 (Vilsmeier reagents), with each alkyl substituent reacting with only one molecule of the electrophile. The resulting aminoalkenyltriazines 4, 5 and 6 are partially or fully hydrolysed to corresponding formylation products. The latter exist either in enol or in unusual acylenamine tautomeric structures 10, 12 , and 13 , depending on the number of enamine or enol units found in the molecule. Reaction of triazines 1 with chlorobenzylidene iminium salts 16 gives monoiminobenzoylation to enaminotriazines 17 .     

High precision measurements of the hyperfine structure of seven metastable atomic states of57Fe by laser-Rf double-resonance

The hyperfine structure of the metastable atomic states (3d ⁷4s)⁵ F _2,3,4,5 and (3d ⁷ 4s)³ F _2,3,4 of⁵⁷Fe has been measured using theABMR- LIRF method (atomic beam magnetic resonance detected by laser induced resonance fluorescence). From these measurements the following hfs constantsA of the magnetic dipole interaction have been obtained (corrected for second order effects):A(⁵ F ₂)=55.994(7) MHzA(⁵ F ₃)=69.632(5) MHzA(⁵ F ₄)=78.435(4) MHzA(⁵ F ₅)=87.246(3) MHzA(³ F ₂)=143.328(4) MHzA(³ F ₃)=50.602(10) MHzA(³ F ₄)=13.456(5) MHz     

Critical evaluation of additivity schemes for estimating heats of atomization

Additivity schemes for estimating heats of formation and heats of atomization of alkanes and halo- alkanes are scrutinized. A least squares analysis of the heats of atomization of alkanes leads to a revision of the values of the parameters. The improvement in the estimated heats of atomization over the values obtained with parameters previously suggested amounts to at least 100%. The reasons for the deviations from the experimental values are discussed. These parameters can be transfered to haloalkanes. Additional parameters necessary for estimating heats of atomization of haloalkanes are also obtained through least squares analyses.