ZnII and CdII Metal Organic Frameworks Based on 2-Methyl-6-oxygen-1,6-dihydro-3,4'bipyridine-5-carbonitrile

To investigate the coordination chemistry of modbc (2-methyl-6-oxygen-1,6-dihydro-3,4'-bipyridine-5-carbonitrile) with Zn^II and Cd^II salts under the solvothermal conditions, six new MOFs with the formulas [Zn(modbc)₂(mpa)]_n ( 1 ), [Zn(modbc)(mpa)(H₂O)]_n ( 2 ), [Zn(modbc)(pa)_0.5(H₂O)]_n ( 3 ), [Cd(modbc)(pa)_0.5(H₂O)]_n ( 4 ), [Zn(modbc)₂(tpa)]_n ( 5 ), and [Cd(modbc)₂(pda)(H₂O)]_n ( 6 ) (mpa = m-phthalic acid; pa = pyromellitic acid; tpa = terephthalic acid; pda = pentane diacid) were successfully synthesized by solvothermal reaction and fully characterized by elemental analysis, IR spectroscopy, single crystal, powder X-ray diffraction, thermal and photoluminescence properties. Though MOFs 3 and 4 have the same structure, we have obtained three different kinds of coordination configurations by the X-ray diffration analysis. Compared with 1 and 2 , coordination water has no effect on the solid fluorescence emission of MOFs. It is worth noting that the fluorescence intensity of 3 containing central Zn^II atoms is very strong, whereas that of isomorphism 4 containing central Cd^II atoms has almost no fluorescence emission, showing that metal ions have very important influence on the fluorescence emission. Further, we found that solvents had an important effect on the fluorescence emission in liquid fluorescence of MOFs 1 – 6 .     

Gold‐Catalyzed Diastereoselective Cycloisomerization of Alkylidene‐Cyclopropane‐Bearing 1,6‐Diynes

An unprecedented gold‐catalyzed diastereoselective cycloisomerization of 1,6‐diynes bearing an alkylidene cyclopropane moiety has been developed. This methodology enables rapid access to a variety of 1,2‐trimethylenenorbornanes, which are important building blocks in the preparations of abiotic and sesquiterpene core structures.     

Gold(I)‐Catalyzed Cycloisomerization of 3‐Alkoxyl‐1,6‐diynes: A Facile Access to Bicyclo[2.2.1]hept‐5‐en‐2‐ones

A novel gold‐catalyzed cycloisomerization of 1,6‐diynes was achieved, providing an atom‐economic approach to a diverse set of bicyclo[2.2.1]hept‐5‐en‐2‐ones in moderate to good yields. With unsymmetrical starting materials with two different internal alkynyl substituents, to some extent, the regioselectivity could be controlled by both electronic and steric factors. This unprecedented reactivity pattern may inspire new and unconventional strategies for the preparation of bridged ring systems.     

Electrosynthesis of 1-indanones

The recent electrocatalytic three-component annulation-halosulfonylation of 1,6-enynes toward 1-indanones is highlighted.     

Synthesis and cyclizations of 1-azapolyene derivatives

Imminium salts of enaminonitriles with polyenals gave stable 1-azapolyenes, which could be readily transformed to benzo- and indoloquinolizines in 1,6-electrocyclizations. Azatrienes and azatetraenes with formaldehyde and primary amines afforded pyrimido[6,1-a]isoquinolines.     

Synthese arylsubstituierter 2-Pyrimidinamine,Dihydro-2-pyrimidinamine und Pyrimido[1,2-a]pyrimidine durch Reaktion von Guanidin mit Chalkonen

4- and 4-methoxy-, 4-hydroxy- and 2-hydroxychalcone4 e,k,f andg, respectively, are transformed by action of guanidine in benzene to yield 4-(4-methoxyphenyl)-6-phenyl-2-pyrimidinamine (6 e=6 k) and hydroxyphenylpyrimidinamines6 f andg, respectively. In contrast, 4- and 4-chlor-, 4-brom- and 4-phenylchalcone4 h,l–n resp. react with guanidine under analogous conditions to give 4,6-diaryl-1,4-dihydro-2-pyrimidinamines5 h,l–n. The bases5 h,l–n also tend to aromatize, but they can be stabilized by transformation into salts5 h,l–n · HCl with hydrochloric acid. Heating of5 n inDMF under atmospheric oxygen yields 4-(4-biphenyl)-6-phenyl-2-pyrimidinamine (6 n). Action of guanidine on 4-nitrochalcone4 o in chloroform affords 2-amino-4-nitrophenyl-6-phenyl-tetrahydro-4-pyrimidinol8 o, which is transformed by hydrochloric acid into 6-nitrophenyl-dihydropyrimidinamine-hydrochloride5 o · HCl. Treating of the latter with sodiummethylat in methanol yields the very stable dihydropyrimidinamine5 o. Action of guanidine on 4-chlor- and 4-bromchalcone4 h andm respectively (in addition to5 h andm) yields 2,4,6,8-tetraaryl-1,4-dihydro-2H-pyrimido[1,2-a]pyrimidines7 h andm, respectively.

Herrn Prof. Dr.Erwin Schauenstein mit den besten Wünschen zum 65. Geburtstag gewidmet.     

Open Chain Chiral Macrolide Building Blocks by Opening of Deoxygenated 1,6-Anhydrosugars with 1,3-Propanedithiol

Chiral building blocks for macrolides and related natural products are obtained from 1,6-anhydrosugars by conversion of the bicyclic acetals 2 or 12 into the open chain chiral 1,3-dithianes 6 and 13. Branched precursors can be obtained by opening of the ?erný epoxide 1 with the 1,3-dithiane anion to yield 7, followed by ring opening with 1,3-propanedithiol to the bis-1,3-dithiane 8.     

Direct access to α,α′-diarylated ketones through N-heterocyclic carbene-catalyzed 1,6-addition of aromatic aldehydes to para-quinone methides

N-Heterocyclic carbene-catalyzed 1,6-addition of aromatic aldehydes to para-quinone methides has been developed. This method could efficiently furnish α,α′-diarylated ketones with good to high yields, which contain various functional groups.