144994-01-4

Upstream product

• 99747-72-5 2,6,6-trimethylcyclohex-1-en-1-yl trifluoromethanesulfonate 
• 62054-49-3 ethyl (E)-3-formyl-2-butenoate 
• 144950-81-2 <(E,E)-4-(2',6',6'-trimethylcyclohex-1'-en-1'-yl)buta-1,3-dien-1-yl>boronic acid 
• 144950-83-4 ethyl (E,E)-5-iodo-3-methylpenta-2,4-dienoate 

Relevant academic research and scientific papers

A comprehensive survey of Stille-type C(sp2)-C(sp2) single bond forming processes in the synthesis of retinoic acid and analogs

The synthesis of the retinoid skeleton has been exhaustively explored using the Stille coupling for the formation of the side- chain single bonds. On employing the experimental catalytic conditions developed by Farina [Pd2(dba)3, AsPh3, NMP] we have modified the electronic and steric requirement of the coupling partners, alkenyl stannanes and electrophiles (alkenyl iodides and triflates). The comprehensive survey afforded appropriately matched components for every bond formation considered. Moreover, from the comparison of the reactivities of different coupling partners with different degrees of steric hindrance, the sensitivity of the Stille coupling to steric effects was confirmed. Besides providing a variety of building blocks for retinoid synthesis, the study highlights some trends that might be useful for the application of the Stille reaction to the synthesis of unsubstituted conjugated polyenes.

General synthesis of retinoids and arotinoids via palladium-catalyzed cross-coupling of boronic acids with electrophiles

A novel approach to the synthesis of retinoids and arotinoids (including heterocyclic analogs) is described which is based on the thallium-accelerated palladium-catalyzed cross-coupling of boronic acids with a variety of electrophiles (the Suzuki reaction).

Stereospecific Synthesis of 9-Demethylretinoids via Palladium-Catalyzed Vinylboronic Acid-Vinyl Iodide Cross Coupling

A stereospecific synthesis of 9-demethylretinoids with either trans or 11-cis geometries, based on the thallium-accelerated palladium-catalyzed cross-coupling reactions of (E)-1-alkenylboronic acid and (E) or (Z)-alkenyl iodides, is described.