Malins. has also reported an in situ synthesis of DMF•SO3 complex using the strategy of the addition of methyl chlorosulfate to DMF at 0 °C. This reaction is exothermic leading to the formation of chloromethane as a side product reaction. This protocol was initially investigated on the methylα-glucoside following the optimised conditions; methyl chlorosulfate (1.1 eq./OH) at 0 °C for 1 h affording the methyl-α-glucoside tetrasulfate in 47% isolated yield. This protocol was further explored on a wide range of small molecules including amino acids, disaccharide, steroids, and acid-sensitive substrates (Scheme 15). Scheme 15. The sulfation reaction of methyl-α-glucoside using methyl chlorosulfate and DMF protocol. Scope of sulfated small molecules with methyl chlorosulfate, sodium Boc-Serine methyl ester sulfate (1), sodium Fmoc-L-Serine methyl ester sulfate (2), sodium Boc-tyrosine methyl ester sulfate (3), sodium β-estradiol disulfate (4), and sodium scymnol persulfate . a conversion percentage calculated by 1 H NMR spectroscopy.