Stereoselective synthesis of MaR2_{n-3 DPA}

Highlights

• The first total synthesis of MaR2_{n-3 DPA} is presented.

• Synthetic and natural materials of MaR2_{n-3 DPA} were matched using LC/MS-MS MRM analysis.

• The key reactions were Wittig- and Takai-olefination reactions and the Z-stereoselective Lindlar reduction.

• The absolute configuration of MaR2_{n-3 DPA} was established.

Abstract

The first total synthesis of the n-3 docosapentaenoic derived oxygenated product MaR2_{n-3 DPA} has been achieved. The 13R and 14S stereogenic centers were introduced using 2-deoxy-d-ribose in a chiral pool strategy. The geometry of the Z,E,E-triene moiety was prepared using highly E-selective Wittig- and Takai-olefination reactions as well as the Z-stereoselective Lindlar reduction. LC/MS-MS data of synthetic MaR2_{n-3 DPA} matched data for the biosynthetic formed product that enabled the configurational assignment of this oxygenated natural product to be (7Z,9E,11E,13R,14S,16Z,19Z)-13,14-dihydroxydocosa-7,9,11,16,19-pentaenoic acid.