New analogues of brassinolide biosynthetic precursors with three deuterium atoms at non-exchangeable positions have been synthesized to be used as standards for quantification of natural brassinosteroids by liquid chromatography-mass spectrometry. [26-2H3](22R,23R,24S)-22,23-Dihydroxy-6β-methoxy-24-methyl-3α,5-cyclo-5α-cholestane was used as a starting material for the preparation of campestane derivatives having a 22R,23R-diol functionality and either a hydroxy or keto group at C-3 and labeled at C-26. The mass spectrometric behavior of the newly synthesized compounds has been studied.
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