Retracted Article: Synthesis of deuterated isopentyl pyrophosphates for chemo-enzymatic labelling methods: GC-EI-MS based 1,2-hydride shift in epicedrol biosynthesis

Abstract

The cyclisation mechanism of epicedrol cyclase elucidated based on GC-EI-MS fragmentation of specific deuterated (2H) epicedrol analogues. The chemo-enzymatic method was applied for the synthesis 8-position-2H-farnesyl pyrophosphate synthesis.

Synthesis of the biologically important dideuterium-labelled adenosine triphosphate analogue ApppI(d2)

“…Synthesis of 3-methylbut-3-en-1-yl-1,1- d 2 4-methylbenzenesulfonate (4) [ 28 ] : 3-Methylbut-3-en-1,1- d 2 -1-ol ( 3 , 415 mg, 4.7 mmol) was dissolved in dry acetonitrile (5 mL), and distilled pyridine (375 µL, 368 mg, 4.7 mmol) and tosyl chloride (900 mg, 4.7 mmol) were added. Then, the reaction mixture was stirred for 4 h at room temperature before being evaporated to dryness in vacuum.…”

“…According to the 1 H NMR spectrum, the product purity was about 88%, which was considered to be pure enough to be used in the next step. Synthesis of 3-methylbut-3-en-1,1-d 2 -1-ol (3) [28]: LiAlD 4 (320 mg, 7.6 mmol, 0.5 equiv) was added to dry and cold (0-3 °C) diethyl ether (15 mL) in an ice-water bath, and 3-methylbut-3-enoic acid (2, 1.5 g, 15 mmol), dissolved in dry diethyl ether (5 mL), was added in small portions with vigorous stirring. After completed addition, the ice-water bath was removed, and the reaction mixture was stirred for 3 h at room temperature before it was cooled again to 0-3 °C.…”