Nitrogen-functionalized Isohexides in Asymmetric Induction

Abstract

Biosourced isohexides have attracted the considerable attention of both the academic and industrial chemistry communities over the last 50 years. This highlight focuses on the synthesis of nitrogen-containing isohexides and their applications in asymmetric catalysis.

2-{(E)-{{(R)-1-[(1R,5S,6R)-3,3-Dimethyl-2,4,7-trioxabicyclo[3.3.0]octan-6-yl]ethyl}imino}methyl}-6-{[(diphenylphosphino)oxy] phenyl}palladium(II) chloride

“…Some of them have been synthesized by Xia for Suzuki or Kumada type couplings [16][17][18]. As isohexide derivatives have shown their efficiency as ligands in organometallic catalysis or as organocatalysts [19,20], we report herein the synthesis of an optical active non-symmetrical iminophosphinite PCN pincer palladium (II) complex derived from isosorbide, which is a sustainable material.…”

Ir–Na cooperativity controls the diastereoselectivity of borrowing hydrogen C–C alkylation on isosorbide: synthesis methodology and mechanistic investigation

“…12 Thus, the functionalization of isosorbide derivatives often requires a prior step of protection of one of the two hydroxyl groups. 13 Although isosorbide functionalization into amines has been widely described using classical multi-step strategies (alcohol activation by a tosylate followed by nucleophilic substitution with an amine), 13 greener alternatives must be considered nowadays. In this context, N -alkylation of ammonia with isohexides using the borrowing hydrogen (BH) methodology was successively reported by Beller, 14 Vogt 15 and Rose.…”

Diastereoselective Iridium-Catalyzed Amination of Biosourced Isohexides Through Borrowing Hydrogen Methodology

“…Isosorbide and isomannide have been used for the synthesis of biocompatible polymers as well as pharmaceutical compounds such as isosorbide dinitrate (Isordil) . Over the last decades, functionalization of these biosourced isohexides into corresponding amines has also attracted considerable interest for polymer applications and for asymmetric induction in organic synthesis (auxiliaries, ligands, and organocatalysts). Reported synthesis of isohexide-based amines involved the use of highly reactive leaving groups, such as tosylates as a given example (Scheme a).…”