Asymmetric synthesis of 2,3-dihydrofurans and of unsaturated bicyclic tetrahydrofurans through alpha-elimination and migratory cyclization of silyloxy alkenyl aminosulfoxonium salts. Generation and intramolecular O,Si-bond insertion of chiral disubstituted beta-silyloxy alkylidene carbenes

Treatment of the bis(allylsulfoximine)titanium complexes derived from the beta-methyl-substituted acyclic allylic sulfoximines 13a and 13b with aldehydes gave with high selectivities the corresponding sulfoximine-substituted homoallylic alcohols which were isolated as the silyl ethers 15a-h. Methylation of sulfoximines 15a-h afforded the aminosulfoxonium salts 5a-h which upon treatment with LiN(H)tBu gave in high yields the enantio- and diastereomerically pure silyl-substituted 2,3-dihydrofurans 4a-h. Treatment of the titanium complexes derived from the cyclic allylic sulfoximines 17a, 17b, and ent-17c with p-MeOC(6)H(4)CHO delivered with high selectivities the corresponding sulfoximine-substituted cyclic homoallylic alcohols which were isolated as the silyl ethers 18a, 18b, and ent-18c, respectively. Methylation of sulfoximines 18a, 18b, and ent-18c furnished the aminosulfoxonium salts 8a, 8b, and ent-8c, respectively, whose treatment with LiN(H)t-Bu gave the enantio- and diastereomerically pure fused bicyclic 2,3-dihydrofurans 6a, 6b, and ent-6c, respectively, in good yields. It is proposed that the 1-alkenyl aminosulfoxonium salts 5a-h, 8a, 8b, and ent-8c react with the base under alpha-elimination and formation of the acyclic and cyclic beta-silyloxy alkylidene carbenes 2a-h, 7a, 7b, and ent-7c, respectively, which then undergo a 1,5-O,Si-bond insertion and 1,2-silyl migration. The cyclic aminosulfoxonium salts 8a, 8b, and ent-8c upon treatment with 1,8-diazabicyclo[5.4.0]-7-undecene did not undergo an alpha-elimination but suffered a novel migratory cyclization with formation of the enantio- and diastereomerically pure bicyclic tetrahydrofurans 9a, 9b, and ent-9c, respectively. It is proposed that the 1-alkenyl sulfoxonium salts 8a, 8b, and ent-8c are isomerized to the allylic aminosulfoxonium salts 10a, 10b, and ent-10c, respectively, which then suffer an intramolecular substitution of the (dimethylamino)sulfoxonium group by the silyloxy group followed by a desilylation. The syntheses of the 2,3-dihydrofurans 4a-h, 6a, and 6b and of the tetrahydrofurans 9a and 9b are accompanied by the formation of sulfinamide 16 of >or=98% ee, which can be converted via sulfoxide 28 of >or=98% to the starting sulfoximine 11 of >or=98% ee.     

Über die bei hohen Ansäuerungsgraden auftretenden Polymolybdat-Typen,insbesondere zur Frage der „Dekamolybdate”︁ und „Phase C”︁-Polymolybdate

On the Polymolybdate Types Occurring at High Degrees of Acidification, with Particular Reference to the “Decamolybdates” and “Phase C” Polymolybdates It is shown that in the range of high acidification (> 1.6H⁺/MoO₄^2?) of aqueous molybdate solutions only two types of solid polymolybdates occur, namely the 36-molybdate and the “decamolybdate” types. These types can be most conveniently identified by their Raman spectra and also by some other characteristics. All the other polymolybdate types proposed in the literature for this range of acidification (“hexamolybdates”, “octamolybdates”, “dodecamolybdates”, “16-molybdates”, a 19-molybdate, the large group of polymolybdates characterized by a wide range of b in the general formula M₂O · bMoO₃ · cH₂O, “phase C” polymolybdates, a “hexagonal hydrate of molybdenum trioxide”, a “reactive molybdic acid”, “NH₃(MoO₃)₃”, and others) can be assigned to one of these two types. The most important reason for the erroneous assignments in the literature is the isomorphous exchange of varying quantities of the alkali or alkaline earth metal cations by H₃O⁺ in the crystal structure, occurring in the highly acidic solutions, particularly with the small cations. This cannot be recognized by the presently available methods of investigation and, hence, leads to the creation of new polymolybdate types. Another reason causing some of the confusion is the assignment of virtually identical X-ray diffraction data to two different types of lattices, a hexagonal and cubic lattice.     

Sulphur substituted organotin compounds : VII. Charge transfer interactions of arylthiomethyl(triphenyl)tin compounds with tetracyanoethylene

Thermolysis of η²-benzoyl(phenyl)zirconocene yields the η²-benzophenonzirconocene complex 2, isolated as a dimer. 2 exhibits an ambivalent reactivity pattern. The formation of five-membered metallacycles from 2 and olefinic hydrocarbons possibly proceeds analogous to reactions of “normal” metalolefin π-complexes. However, both reactions with the electron-deficient olefins dimethylfumarate and -maleate and the behavior towards electrophilic and protic reagents as well as aromatic hydrocarbons might be interpreted in terms of a metallaoxirane-character of 2.     

Biologisch aktive 3,3-Dimethylbicyclo[2.2.2]octane: Synthesen in der Isocamphanreihe, 35. Mitt.

Summary The bicyclo[2.2.1]- and [2.2.2]-systems are part of numerous biological active substances. Continuing our syntheses in the isocamphane series the homologous isocamphanes of mecamylamine (1 a) and of the fungicidal bicyclic compound2 were synthesized. Furthermore the syntheses ofE-homoisosantalene (15) andE,E-homoisosantalol (16) are described.

     

Accurate determination of low pK values by (1)H NMR titration

The NMR titration methodology to determine acid dissociation constants in aqueous solutions is extended for pK(a) values between 0 and 2, where potentiometric titrations are no longer applicable. (1)H NMR spectra are acquired for single samples of constant acid concentration (e.g. 0.02M), controlled ionic strength (I=1M with HNO(3)/NaNO(3)) and varying pH. To avoid biased pH readings due to the acid error of the glass electrode, true, concentration-based pH values are deduced by combination of the charge balance equation with information from (1)H NMR chemical shifts of the investigated acid. The method has been tested on histidine (pK(1)=1.83+/-0.02) and yielded the dissociation constant of dichloroacetic acid (pK=1.06+/-0.01) for the first time with good accuracy and precision. Dichloroacetic acid is recommended as an NMR spectroscopical "indicator molecule" for in situ monitoring the pH in strong acidic solutions of other equilibrium systems.     

Fragmentation of 1-aryl-5-(2-dialkylaminovinyl)-1H-tetrazoles upon electron impact

The mass spectrometric behaviour of 1-aryl-5-(2-dialkylaminovinyI)-lH-tetrazoles was studied, especially 1-phenyl-5-(2-dimethylaminovinyl)-l H-tetrazole as a typical example of D- and ¹⁵N-labelled derivatives revealed a rearrangement via a carbodiimide-like intermediate ion.     

Synthesis of enantiopure axially chiral C3-symmetric tripodal ligands and their application as catalysts in the asymmetric addition of dialkylzinc to aldehydes

The enantioselective synthesis of a novel-type C(3)-symmetric tripodal ligand that is composed of a central mesitylene-derived core and three functionalized, axially chiral biaryl subunits is described. The triol (M,M,M)-3 is a suitable catalyst for the enantioselective addition of dialkylzinc to various aromatic aldehydes with asymmetric inductions of up to 98% ee.     

A new class of C1-symmetric monosulfoximine ligands for enantioselective hetero Diels-Alder reactions

Quinoline-based C1-symmetric sulfoximines have been used as chiral ligands in copper-catalyzed asymmetric hetero Diels-Alder reactions leading to cycloadducts with up to 96% ee.     

Stereochemistry of isoplagiochin C, a macrocyclic bisbibenzyl from liverworts

Cyclic bisbibenzyls, like isoplagiochins C (1) and D (2), are stereochemically intriguing molecules: Although not equipped with any of the traditional stereogenic elements that render molecules conformationally stable per se, they are sometimes isolated in an optically active form and are thus chiral at room temperature. The paper describes quantum chemical calculations, in particular investigations of the conformational space and molecular dynamics simulations, showing that the helicity is a property of the entire molecule, whose ring strain makes the molecule configurationally stable overall, with (formally) three stereogenic elements (two biaryl axes and one helical stilbene unit). Only one of the biaryl axes (the 'upper' one, joining C-12' and C-14) has a stable configuration, leading to a population of four interconverting diastereomers, yet without racemization at room temperature. On the basis of these conformational and dynamic calculations, the circular dichroism spectrum of isoplagiochin C (1) was calculated, leading to the first assignment of the absolute configuration of a cyclic bisbibenzyl. Accordingly, 1 has the P-configuration at the stereochemically stable biaryl axis and constitutes a mixture of diastereomers with respect to the other biaryl axis and the helical stilbene unit. From the temperature dependence of the racemization rates, an enantiomerization barrier of 101.6 kJ/mol was determined. Likewise, for the first time for cyclic bisbibenzyls, the enantiomeric ratio of this natural product was determined, by chromatography on a chiral phase with CD-coupling. Accordingly, 1 from Plagiochila deflexa is not enantiomerically pure, but occurs in a 85:15 ratio in favor of the enantiomer that has the P-configuration at the stereochemically stable axis.     

Zur Synthese von fungizid wirksamen Isocamphanderivaten: Synthesen in der Isocamphanreihe, 34. Mitt.

Summary Some esters of isocamphenilanic acid (4) have been prepared and tested for their fungicidal and insecticidal activity. Esters of various acids with isocamphanyl ethylalcohol (5) have also been synthesized and included in the fungicidal/acaricidal/insecticidal screening programme. All esters bear a geminal dimethyl group at C-3 of the bicyclus which is important because of its shielding effect.