Expanding the Scope of Biomass‐Derived Chemicals through Tandem Reactions Based on Oxorhenium‐Catalyzed Deoxydehydration

Abstract

New modes of DODH: Oxorhenium compounds act as deoxydehydration(DODH)/acid dual-purpose catalysts to transform biomass-derived diol substrates into a variety of commodity chemical precursors. The power of this approach is highlighted by a tandem [1,3]-OH shift/DODH of 2-ene-1,4-diols and 2,4-diene-1,6-diols, and by a DODH/esterification sequence of sugar acids to unsaturated esters for the production of polymers and plasticizers.

Rhenium‐Catalyzed Deoxydehydration of Diols and Polyols

“…In addition to this transformation, they showed that not only erythritol and 3butene-1,2-diol but also cis-2-butene-1,4-diol could be converted into 1,3-butadiene. [24] After the publication of the Cook and Andrews paper, no new contributions to the rhenium-catalyzed DODH of diols were made until 2009, where Abu-Omar and co-workers showed that CH 3 ReO 3 catalyzed the H 2 -driven transformation of vicinal diols (and epoxides) into the corresponding alkenes (Table 1, entry 2). [24] After the publication of the Cook and Andrews paper, no new contributions to the rhenium-catalyzed DODH of diols were made until 2009, where Abu-Omar and co-workers showed that CH 3 ReO 3 catalyzed the H 2 -driven transformation of vicinal diols (and epoxides) into the corresponding alkenes (Table 1, entry 2).…”

“…Their DFT calculations of the mechanism were similar to those of Wang, [17] the most important addition being that the second DODH was much faster than the first. [24,25] Both pathways in Scheme 8 rely on the ability of the oxorhenium complexes to cycle between the oxidation states + V and + VII, but a fundamentally different mechanism involving an oxorhenium(III) diolate has recently been proposed by Abu-Omar and co-workers. Rhenium-catalyzed DODH of glycerol to allyl alcohol driven by oxidation of glycerol itself to 1,3-dihydroxyacetone; the reaction was performed in neat glycerol at 165 8C.…”

“…[11] It has been highlighted twice, [12,13] been the subtopic of two reviews, [14,15] and recently both the uncatalyzed and transition-metal-catalyzed DODH were treated in a book chapter; [16] within the past two years, more than ten papers dealing with mechanistic investigations [17][18][19] and the development of new rhenium-based catalysts, [20,21] reductants, [22,23] substrates, [24,25] and catalysts based on other elements [26][27][28] have been published, and we therefore think that the time has come for a dedicated Minireview. [11] It has been highlighted twice, [12,13] been the subtopic of two reviews, [14,15] and recently both the uncatalyzed and transition-metal-catalyzed DODH were treated in a book chapter; [16] within the past two years, more than ten papers dealing with mechanistic investigations [17][18][19] and the development of new rhenium-based catalysts, [20,21] reductants, [22,23] substrates, [24,25] and catalysts based on other elements [26][27][28] have been published, and we therefore think that the time has come for a dedicated Minireview.…”

Highly Efficient Chemical Process To Convert Mucic Acid into Adipic Acid and DFT Studies of the Mechanism of the Rhenium‐Catalyzed Deoxydehydration

“…Recently, the wellknown deoxydehydration (DODH) reaction has been successfully applied to the conversion of polyols, including sugar alcohols, into conjugated alkenes. [14] In the present work, we report the highly efficient conversion of mucic acid (1) into muconic acid (2) through a DODH reaction catalyzed by an oxorhenium complex. [13] Very recently, Shiramizu and Toste reported the conversion of mucic acid into adipic acid ester, by using a DODH and hydrogenation reaction, in moderate yields.…”

Synthesis of Cyclopentadienyl‐Based Tricarbonyl Rhenium Complexes and Some Unusual Reactivities of Cyclopentadienyl Substituents

“…[1,2] Among these, lignocellulosic biomass holds promise for the sustainable production of commodity chemicals and other building blocks. [14][15][16] the lithium salt of the deprotonated ligand (Cp′Li), and the aryl groups decreased the electron donation. Thus, the synthesis of industrially relevant chemical building blocks requires several consecutive dehydroxylation reactions through reductive deoxygenation methods.…”