: In this review, we examined the possibility that some halogenated organic derivatives were used in the primitive ocean at the beginning of life on Earth. Firstly, we described the existence of extraterrestrial halogenated molecules, then we studied their nonbiological syntheses on the present Earth, especially in volcanic environments. In order to demonstrate the diversity of today’s halogenated biomolecules, representative examples are given and the biosynthesis of some of them is summarized. Finally, we proposed two aspects of the chemistry of halogenated compounds that may have been useful en route to biomolecules, firstly the use of methyl chloride as the first methylation reagent, secondly the synthesis and use of α-chloro-carbonyl derivatives.

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