(682h) Rhenium Catalyzed Conversion of Sugar Acids to Adipates Via Deoxydehydration and Hydrogen Transfer Using Isopropyl Alcohol

Rhenium Catalyzed
Conversion of Sugar acids to Adipates via Deoxydehydration and Hydrogen
Transfer using Isopropyl Alcohol

Jun Hee Jang¹ and Mahdi
M. Abu-Omar¹*

¹ Department of Chemical Engineering and Department of
Chemistry & Biochemistry, University of California, Santa Barbara, CA 93106
(USA)

*mabuomar@ucsb.edu

Making
bulk chemicals from biomass starting materials has gained extensive attention to
satisfy the social demand for sustainability.¹ One
attractive valorization of biomass is the production of dicarboxylic acids and
its derivatives from sugar acids. Adipic acid, a monomer of nylon-6,6
polyamide, is produced 2.6 million tons per year.²
Commercially, its production relies on non-renewable petroleum-derived synthons
and emits significant amount of N₂O.² In
this sense, efficient and environmentally friendly methods for adipic acid
synthesis from biomass feedstocks are highly desired. Conversion of glucose
into adipic acid was achieved by the combination of biocatalysis and
chemocatalysis, but the reported yield is very low.³ While
glucaric acid is used to synthesize adipic acid via catalytic hydrogenation,
this reaction requires harsh conditions including halogen bromide and high
pressure of H₂.⁴ Recently,
deoxydehydration (DODH), which converts vicinal diols to alkenes in the
presence of sacrificial alcohols, has been employed to prepare dicarboxylic
acids or their esters from sugar acids (Scheme 1a). Shiramizu and Toste
reported the conversion of mucic acid to adipates in moderate yields using a
two-step process: (1) the oxorhenium complex-catalyzed DODH and (2) Pd/C-catalyzed
hydrogenation.⁵ Zhang
et al. achieved a higher yield of adipates by one step route (75%) or two steps
route (99%) including DODH and subsequent hydrogenation transfer reaction.⁶

This
sustainable and efficient system, however, requires two catalysts: one
homogeneous catalyst for DODH and one heterogeneous catalyst for hydrogenation.
Besides the use of two different catalysts, the reductants of DODH employed in
the system such as 3-pentanol and 1-butanol are neither cheap nor green. In
very recent years, H₂-driven DODH and hydrogenation have been
investigated to produce adipates from sugar acids with two catalysts working in
tandem by Toste and coworkers.⁷ Herein,
we demonstrate that unsupported ReO_x nanoparticles catalyst affords
not only DODH but also hydrogen transfer reaction with isopropyl alcohol as a
reductant and a solvent. This ReO_x catalyst directly synthesize
adipates from sugar acids in a single step with isopropyl alcohol, a cheap and
green reductant and solvent (Scheme 1b).

Scheme 1.  Conversion of sugar acid into adipates using
(A) previous approach (B) our approach

References

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