An efficient enantioselective synthesis of (2R)-hydroxymethyl glutamic acid and an approach to the (2R)-hydroxymethyl-substituted sphingofungins.
We have developed a short enantioselective synthesis of (2R)-hydroxymethyl glutamic acid (HMG) starting from Garner's aldehyde using an alkylidene carbene 1,5-CH insertion as a method to construct the quaternary stereocenter. A variety of conditions were examined for the oxidative cleavage of the key cyclopentene intermediate and we found that RuCl3/NaIO4 led directly to the desired amino bis-acid product. We were also able to show that oxidative cleavage of the cyclopentene 1,5-CH insertion product could be used to produce the amino acid-containing skeleton of the sphingofungin family of natural products.
Hayes
Christopher J
CJ
School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, United Kingdom. chris.hayes@nottingham.ac.uk
Bradley
Daniel M
DM
Thomson
Nicholas M
NM
D000596:Amino Acids / Q000138:chemical synthesis / Q000737:chemistry; D005231:Fatty Acids, Unsaturated / Q000138:chemical synthesis / Q000737:chemistry; D005971:Glutamates / Q000138:chemical synthesis* / Q000737:chemistry; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D013237:Stereoisomerism
C449086:(hydroxymethyl)glutamic acid; D000596:Amino Acids; D005231:Fatty Acids, Unsaturated; D005971:Glutamates; C078943:sphingofungin E