Direct Amination of Isohexides via Borrowing Hydrogen Methodology: Regio‐ and Stereoselective Issues

Abstract

The regio and diastereoselective direct mono or diamination of bio-based isohexides (isosorbide and isomannide) has been developed through borrowing hydrogen (BH) methodology using a cooperative catalysis between an iridium com-[a] Univ Lyon,

Hydrogen Borrowing: towards Aliphatic Tertiary Amines from Lignin Model Compounds Using a Supported Copper Catalyst

“…Prior to reaction, each catalyst is pretreated as described in the experimental section and a fixed amount of catalyst (120 mg, 0.6 wt % versus total loading) was added to the reaction mixture, regardless of metal loading. O ‐xylene is applied as solvent since apolar, non‐hydrogen bonding solvents (e.g., toluene, xylenes or aliphatic hydrocarbons) are commonly used during HB involving substrates containing aromatic entities [20,22,27,57] . They are able (i) to dissolve the substrates and products reasonably well and (ii) do not interfere strongly with the catalysts’ active sites due to their low or absence of Lewis basicity [58] .…”

“…O-xylene is applied as solvent since apolar, non-hydrogen bonding solvents (e.g., toluene, xylenes or aliphatic hydrocarbons) are commonly used during HB involving substrates containing aromatic entities. [20,22,27,57] They are able (i) to dissolve the substrates and products reasonably well and (ii) do not interfere strongly with the catalysts' active sites due to their low or absence of Lewis basicity. [58] For most catalysts, we were able to identify nearly all reaction products, thereby capable of reporting almost the complete mass balances.…”

“…[16,20] The excellent atom-efficiency, with ideally water as sole byproduct, makes this methodology highly appealing. [21] This dehydrogenation-condensation-hydrogenation process is commonly catalyzed by transition metalbased catalysts, both homogeneous (Ir, [22,23] Ru, [24][25][26][27] Cr, [28] Fe, [29] Mn, [30] Ni [15] ) and heterogeneous (Cu, [31,32] Co, [33,34] Ni, [20,35,36] Pd, [37] Ru [38,39] ) as recently reviewed by Kempe et al [40,41] N-alkylation of various alcohols has been reported, starting mostly from NH 3 , [20,33,35,38] and (C-substituted) anilines. [15,[28][29][30]32] Disclosures dedicated to employing primary and secondary alkylamines exist, but are more scarce.…”

Toward Renewable Amines: Recent Advances in the Catalytic Amination of Biomass-Derived Oxygenates

“…280 Furthermore, Ir-complexes were also found active for the amination of isohexides at relatively low temperatures of approximately 100−120 °C (Table 14, entries 3 and 4). 281,282 Monoamination products were synthesized with up to 65−71% yield in toluene. Usually, homogeneous catalysts show good activity for monoamine production in organic solvents; however, recyclability and multistep reactions are still a concern for large-scale reactions.…”

Chemocatalytic value addition of glucose without carbon–carbon bond cleavage/formation reactions: an overview

“… 210 In 2019, a novel two-step synthesis of isomannide diamine (IMDAM) was reported. 211 In the first step, the –OH groups in IS were replaced with benzylamine using cooperative catalysis between an iridium complex and a Brønsted acid. The benzyl group was deprotected in the second step by catalytic hydrogenation, forming IMDAM in 59% overall yield.…”