The Increasing Value of Biomass: Moving From C6 Carbohydrates to Multifunctionalized Building Blocks via 5-(hydroxymethyl)furfural

Abstract

Recent decades have been marked by enormous progress in the field of synthesis and chemistry of 5-(hydroxymethyl)furfural (HMF), an important platform chemical widely recognized as the "sleeping giant" of sustainable chemistry. This multifunctional furanic compound is viewed as a strong link for the transition from the current fossil-based industry to a sustainable one. However, the low chemical stability of HMF significantly undermines its synthetic potential. A possible solution to this problem is synthetic diversification of HMF by modifying it into more stable multifunctional building blocks for further synthetic purposes.

Keywords: 5-(hydroxymethyl)furfural; biorefining; carbohydrates; plant biomass; renewable building blocks; sustainable chemistry.

Scheme 1

Lewis‐acid‐catalyzed conversion of aldohexose carbohydrates into C6 furfurals.

Scheme 2

(A) Traditional approach to HMF‐based biorefining through direct derivatization of HMF. (B) Biorefining based on HMF diversification to multifunctionalized building blocks (the scope of this review). The key polyfunctional HMF‐derived building blocks are shown in green to emphasize their importance; the same color code is used in the schemes below.

Scheme 3

CMF‐based synthesis of key HMF derivatives.

Scheme 4

Synthesis of multifunctional building blocks from CMF.

Scheme 5

HMFCA as a multifunctional building block.

Scheme 6

Aminated polyfunctional derivatives of HMF and AMF.

Scheme 7

Building blocks obtained from HMF by C−C coupling.

Scheme 8

Synthetic potential of the HMF‐derived furfurylidene ketones.

Scheme 9

(A) Products of hydrogenative hydrolytic ring‐opening in BHMF. (B) Synthetic potential of HHD.

Scheme 10

(A) General routes to polyfunctional building blocks via oxidation of HMF. (B) Potential of compounds 41 and 46 as precursors for the synthesis of heterocycles.

Scheme 11

Butenolide 39 a as a multifunctional building block.

Scheme 12

Hydrothermal recyclization of HMF into BTO and its synthetic potential.

Scheme 13

Synthesis of trisubstituted furanic building blocks by CH‐functionalization of FDCA esters or monoamides.

Scheme 14

Ru‐catalysed CH‐activation of HMF‐derived imines. TBS=tert‐butyldimethylsilyl. Bnep=boronic acid neopentylglycol ester. BA=benzylideneacetone. ^a) Contain 2‐(piperidin‐1‐yl)ethyl as a directing group. PMP=p‐methoxyphenyl.