Search

Electrically conducting organic salts, known for over 60 years, have recently demonstrated new abilities to convert waste heat directly into electrical power via the thermoelectric effect. Multiple opportunities are emerging for new structure–property relationships and for new materials to be obtained through synthetic organic chemistry. This review highlights key aspects of this field, which is complementary to current efforts based on polymeric, nanostructured or inorganic thermoelectric materials and indicates opportunities whereby mainstream organic chemists can contribute.1 What Are Thermoelectrics? And Why Use Them?2 Current Organic and Hybrid Thermoelectrics3 Unique Materials from Tetrathiotetracenes4 Synthesis of Tetrathiotetracenes5 Materials and Device Applications6 Future Perspectives

The asymmetric copper-catalyzed conjugate addition to α-alkylidene cycloalkanones, substituted at their terminal position with aromatic and aliphatic groups, is reported. While high enantioselectivity is reached using chiral phosphoramidite ligands, with R3Al reagents, moderate diastereoselectivity was observed upon hydrolysis of the aluminium enolates. A Grignard reagent also react with high diastereo­selectivity.

Conjugate alkynylation of acyclic enones using sp-hybridisedpotassium organotrifluoroborates in the presence of BF 3 ˙OEt 2 israpidly attained. The simplicity of the processes is suitable forthe preparation of small compound libraries.

A discussion focusing on the benefits of considered forethought in proposing new asymmetric catalytic reactions is presented based on the author’s experiences in the areas of copper-promoted 1,4-addition and S N 2′ chemistry and in the area of group 10 catalysed coupling reactions of organoaluminium reagents with aldehydes and allylic halides. While high-throughput methods have become the norm for attaining practical procedures in catalytic asymmetric chemistry appropriate strategic planning should not be abandoned in the conception of new catalytic processes.

High temperature (110-120 ˚C) direct reactionof ArI (Ar = Ph, 1-C 10 H 7 , 3-Tol)with aluminium powder in the presence of HgCl 2 (1 mol%)or liquid gallium metal (10 mol%) leads to quantitativeconversion to the aryl sesquiiodides Al 2 Ar 3 I 3 .The latter, highly Lewis acidic, compounds are effective in openingof cyclic ethers and direct ester to amide conversions.

In the presence of the monothiobinaphthol (MTB) ligand aryl ketones are allylated by mixtures of Sn(CH 2 CH=CH 2 ) 4 / RSn(CH 2 CH=CH 2 ) 3 (R = Et, Bu) in high e.e. The presence of water suppresses racemic background allylation.