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Upstream product

• 204917-54-4 (1R,9R)-10,10-Dimethyl-6-aza-tricyclo[7.1.1.0^2,7]undeca-2⁽⁷⁾,3,5-triene-5-carboxylic acid ethyl ester 
• 918938-00-8 (1R,9R)-5-Bromo-10,10-dimethyl-6-aza-tricyclo[7.1.1.0^2,7]undeca-2⁽⁷⁾,3,5-triene 
• 68-12-2 N,N-dimethyl-formamide 
• 34413-88-2 pinocarvone 
• 204917-60-2 (-)-(5R,7R)-5,6,7,8-tetrahydro-5,7-(9,9-dimethylmethano)quinoline-2-carboxylic acid 
• 946-07-6 1-(2-(furan-2-yl)-2-oxoethyl)pyridinium bromide 
• 15109-94-1 1-(2-furyl)-2-bromoethanone 
• 172031-87-7 (1R,9R)-5-Furan-2-yl-10,10-dimethyl-6-aza-tricyclo[7.1.1.0^2,7]undeca-2⁽⁷⁾,3,5-triene 
• 330808-99-6 (1R,9R)-10,10-Dimethyl-6-aza-tricyclo[7.1.1.0^2,7]undeca-2⁽⁷⁾,3-dien-5-one 

Relevant academic research and scientific papers

New synthetic routes toward enantiopure nitrogen donor ligands

(Chemical Equation Presented) New polypyridylic chiral ligands, having either C3 or lower symmetry, have been prepared via a de novo construction of the pyridine nucleus by means of Kroehnke methodology in the key step. The chiral moieties of these ligands originate from the monoterpen chiral pool, namely (-)-α-pinene ((-)-14, (-)-15) and (-)-myrtenal ((-)-9, (-)-10). Extension of the above-mentioned asymmetric synthesis procedure to the preparation of enantiopure derivatives of some commonly used polypyridylic ligands has been achieved through a new aldehyde building block ((-)-16). As an example, the synthesis of a chiral derivative of N,N-bis(2-pyridylmethyl) ethylamine (bpea) ligand, (-)-19, has been performed to illustrate the viability of the method. The coordinative ability of the ligands has been tested through the synthesis and characterization of complexes [Mn((-)-19)Br2], (-)-20, and [RuCl((-)-10)(bpy)](BF4), (-)-21. Some preliminary results related to the enantioselective catalytic epoxidation of styrene with the ruthenium complex are also presented.

Versatile synthesis of chiral 6-oxoverdazyl radical ligands-new building blocks for multifunctional molecule-based magnets

A versatile synthetic methodology to access the first family of chiral verdazyl N,N′-chelate ligands is described and exemplified by N,N′-dimethyl-, N,N′-di-isopropyl- and N,N′-diphenyl oxoverdazyls bearing two isomers of the pinene-pyridine functional group. Their physical properties were probed by X-band EPR spectroscopy, cyclic voltammetry and DFT calculations. Preliminary reactivity studies show they can act as N,N′-chelate ligands affording a chiral 1:1 complex (3b) with CuCl2, which was characterized by single-crystal X-ray diffraction. Variable temperature EPR studies on (3b) confirm the presence of antiferromagnetic interactions between the spins of the Cu(ii) ion and the verdazyl radical.

Synthesis and characterization of highly conjugated, chiral bridging ligands

This paper describes the synthesis of four chiral derivatives of the electronically highly conjugated tetra-2-pyridylpyrazine (TPPZ) bridging ligand, which are denoted (R)- and (S)-4,5- and 5,6-pineno-tetra-2-pyridylpyrazine (PTPPZ). Preparation of these ligands was undertaken through the use of commercially available, enantiomerically pure (1R)- and (1S)-α-pinene, which was functionalized and subsequently employed in a Kroehnke pyridine synthesis involving a furan-substituted pyridinium salt to yield a chiral, furan-substituted pyridyl intermediate. Oxidative degradation and subsequent reduction of this furan led to a chiral, substituted 2-pyridylaldehyde, which underwent a pyridoin condensation followed by cyclization to produce the final PTPPZ ligands.