New tetrazines substituted by heteroatoms have been synthesized and their electrochemical and photochemical properties investigated. All compounds are reversibly electroactive with standard potentials shifting cathodically according to the donor character of the substituent. The tetrazine derivatives are also fluorescent with maximum emission wavelengths in the range 550–575 nm. Some of them show very long fluorescence lifetimes (several tens of ns) and remain fluorescent in the solid state without major changes in the spectral features. The fluorescence of one of the derivatives can be efficiently quenched by the presence of electron‐rich compounds such as triphenylamines, phenol or anisole, which make them very promising compounds for sensor applications.

[structure: see text] Full conversion and enantioselectivities up to 83% have been obtained in the conjugate addition reactions of diethyl zinc to Michael acceptors catalyzed by well-defined (chiral) copper(I) aminoarenethiolates. Interesting differences between organozinc or Grignard reagents have been found: for cyclic enones R(2)Zn reagents afford better results, whereas earlier work showed that RMgX reagents react more selectively with acyclic enones.

Regioselectivity is an important aspect in the design of organic protocols involving Directed ortho-Lithiation (DoL) of arenes, in particular with those arenes containing heteroatom substituents as directing groups. The DoL of 2-[(dimethylamino)methyl]naphthalene (dman) that proceeds with low regioselectivity was revisited by varying both the nature of the lithiating reagent (either n-BuLi or t-BuLi) and/or the solvent (pentane or diethyl ether); the 3-deuterated substrate, 3-Ddman, was also investigated as a substrate to compare to that of dman. The 3-lithio regioisomer exists as tetranuclear [2-(Me2NCH2)C10H6Li-3]4, 1, both in the solid state (X-ray) and in solution (NMR). The 1-lithio regioisomer, 2a, is insoluble; in the presence of additional coordinating solvents (Et2O) or ligands (dman), it exists as dinuclear [2-(Me2NCH2)C10H6Li-1]2·L (coordinated L = Et2O: 2b, dman: 2c) in apolar solvents. Heating solutions of 2c in toluene-d8 (to 90 °C) induced a surprisingly clean and quantitative 1-lithio to 3-lithio conversion of the 1-lithio-naphthalene isomer. This type of reaction is rare in organolithium chemistry and has obvious significant implications for the design of regioselective DoL protocols; this thus represents the synthetically useful protocol for the DoL of dman in a one-pot/two-step process in toluene solution. The results of the use of 3-Ddman in these reactions gives strong credence to a mechanism involving formation of the heteroleptic species [(2-(Me2NCH2)C10H6-1)(2-(Me2NCH2)C10H6-3)Li2]·[dman], A, as the key intermediate. Intramolecular trans-lithiation takes place with A; dman becomes selectively lithiated at its 3-position, while the formerly 1-lithio-naphthalene fragment, acting as a highly unusual ortho-lithiating reagent, is converted into the N-coordinated amine, dman. In this intramolecular DoL process, free dman can be considered to act as a catalyst.

, and [LiC6H4(CH(Me)N(Me)CH2CH2NMe2-(rac))-2]2 ((rac)-3b) were synthesized and characterized in the solid state and in solution. X-ray crystallographic studies of 2b and (R)-3b and molecular weight determinations of 2b, (R)-3b, and (rac)-3b by cryoscopy in benzene showed that, both in the solid state and in apolar, noncoordinating solvents such as benzene, these compounds exist as discrete dimeric aggregates. For (R)-3b and (rac)-3b the aggregation process of two monomeric aryllithium units to one dimer is highly diastereoselective.