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. 2020 Sep 9;60(1):66–87. doi: 10.1002/anie.202002433

Table 1.

Main reaction types used to modify cellulose REGs and typical reaction conditions covering homogeneous (*) and heterogeneous systems.

Reaction type

Reactants

Medium, pH conditions/catalysis

Temperature, duration

Ref.

ligation

aliphatic/aromatic

hydrazine analogues[a]

aqueous, (mostly) alkaline

25–35 °C, 24–72 h

[76, 77, 78, 79, 80]

DMSO (anhydrous), Ar atmosphere

50–60 °C, 4 days

[109]

hydroxylamines

aqueous, acidic or DMAc/LiCl (2.5 % w/v), Et3N*

40 °C, up to 700 h

[73, 74, 75]

thiosemicarbazide

aqueous, acidic

60–65 °C, 90 min

[20, 52]

NMMO/water (80/20, v/v)*

60 °C, 90 min

[81, 82, 83]

reductive amination

1° amine ligands

+ reducing agent

aqueous buffer, acidic or alkaline

70 °C, 24–72 h

[87, 88, 89, 90]

MeOH/acetic acid

50 °C, 12–16 h

[54]

DMF

RT or 70 °C, 1 or 3 days

[110]

DMAc/LiCl*

70 °C, 24 h

[111]

Pinnick oxidation

& amide coupling

1) NaClO2

1) aqueous, acidic

1) RT, 20–48 h

[22, 88, 89, 103, 104, 105]

2) 1° amine ligands

+ coupling agents

2) aqueous, pH switch to alkaline

2) RT, 2 h–3 d

[88, 89, 103, 104, 105]

aqueous, pH 5

4 °C, 24 h

[22]

Knoevenagel

condensation

1,3‐diketones

aqueous bicarbonate, pH 8.5

80–90 °C, 4–48 h

[75]

[a] Characterized by hydrazine core (NH2‐NH‐R).