Asymmetric Synthesis of 1-Aminopentadecane-3,5,7,9,11,13,15-heptols and of 1,15-Diaminopentadecane-3,5,7,9,11,13-hexols and Derivatives

Abstract

Starting from 2,2¢-methylenedifuran, enantiomerically enriched (98%) (3R,5S,7R,9S,11R,13R)-and (3R,5S,7S,9R,11R,13R)-15-amino-5,7,9,11-tetrahydroxy-3,13-bis-(4-methoxybenzoyloxy)pentadec-1-yl) pivalate were prepared as well as (3R,5R,7R,9R,11S,13S)-1, 15-diamino-5,7,9,11-tetrahydroxypentadeca-3,13-diyl bis(4-methoxybenzoate) and (3R,5S,7S,9S,11R,13S)-1, 15-diaminopentadecane-3,5,7,9,11,13hexol.

A New Efficient Synthesis of Long‐Chain Di‐ and Triaminopolyols

“…Vogel’s group has developed a non‐iterative asymmetric synthesis of fifteen‐carbon 1,3‐polyols and heptahydroxypentadecanals based on the stereoselective functionalization of dialkenes of type meso ‐ 4 7 and (±)‐ threo ‐ 5 ,8which are readily obtained from the bicyclo adducts resulting from the double [4+3] cycloaddition of 2,2′‐methylenedifuran to 1,1,3‐trichloro‐2‐oxyallyl cation (Scheme ) 9. In previous studies, we demonstrated that meso ‐ 4 can be desymmetrized and transformed into polyketides containing amino groups at the terminal positions of the systems 7c. Nevertheless, the synthetic route requires a large number of steps and does not allow the selective introduction of amino groups at internal positions of the polyketide chain.…”