Natural Products Containing 'Rare' Organophosphorus Functional Groups

Area of Science:

• Biochemistry and Molecular Biology
• Natural Product Chemistry
• Bioinorganic Chemistry

Background:

• Organophosphorus compounds are fundamental to cellular processes.
• While phosphate is common, P-N, P-S, and P-C linkages exist in nature.
• These less common linkages play critical, yet often overlooked, biological roles.

Purpose of the Study:

• To categorize natural organophosphorus compounds with P-N, P-S, and P-C bonds.
• To review the biological significance, sources, and biosynthesis of these compounds.
• To challenge the perception of nonphosphate organophosphorus groups as biochemically rare or insignificant.

Main Methods:

• Comprehensive literature review and categorization of natural organophosphorus compounds.
• Analysis of existing data on biological sources, activities, and biosynthesis.
• Review of phosphorylation in unusual amino acids and nucleotide modifications.

Main Results:

• Detailed cataloging of P-N, P-S, and P-C natural organophosphorus compounds.
• Summary of known biological activities and metabolic roles, including N- and S-phosphorylation.
• Highlighting natural phosphorothioate (P-S) and phosphoramidate (P-N) modifications in DNA and nucleotides.

Conclusions:

• Nonphosphate organophosphorus functional groups are not biochemical oddities but play central metabolic roles.
• The prevalence and importance of certain phosphorus groups, especially P-N bonds, are likely underestimated.
• Technological limitations in detection and analysis have historically obscured the full significance of these compounds.