Synthesis of Enantiopure Tertiary Skipped Diynes via One-Pot Desymmetrizing TMS-Cleavage

Malek Nechab (1) , Nicolas Vanthuyne (2)

1 ICR - Institut de Chimie Radicalaire
2 ISM2 - Institut des Sciences Moléculaires de Marseille

Enantiopure tetrasubstituted skipped diynes were readily synthesized from N-protected amino esters upon addition of lithium TMS-acetylide which was found to be desymmetrizing through one-pot selective TMS-cleavage. The deprotection of the TMS group was realized through a one-pot silicon atom attack by the liberated methoxide, which was diastereoselective due to a conformational favorable chelate.

Domaines: Chimie

Malek Nechab, Nicolas Vanthuyne. Synthesis of Enantiopure Tertiary Skipped Diynes via One-Pot Desymmetrizing TMS-Cleavage. Organic Letters, 2012, 14 (15), pp.3974--3977. ⟨10.1021/ol3017462⟩. ⟨hal-01460404⟩