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Enantiopure 2,9‐Dideuterodecane – Preparation and Proof of Enantiopurity
Author(s) -
Mitschke Nico,
Eruçar Gülsera,
Fsadni Miriam H.,
Roberts Amy R.,
Sadeghi Majid M.,
Golding Bernard T.,
Christoffers Jens,
Wilkes Heinz
Publication year - 2021
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.202100360
Subject(s) - chemistry , enantiopure drug , enantioselective synthesis , olefin fiber , decane , hydroxylation , geminal , yield (engineering) , organic chemistry , double bond , stereochemistry , medicinal chemistry , catalysis , materials science , metallurgy , enzyme
( R , R )‐ and ( S , S )‐(2,9‐ 2 H 2 )‐ n ‐Decane were prepared regio‐ and stereospecifically in 25–26 % yield over five steps from commercially available enantiopure ( R )‐ and ( S )‐propylene oxide, respectively. The synthetic procedure involved nucleophilic displacement of ( R )‐ and ( S )‐4‐toluenesulfonic acid 1‐methyl‐4‐pentenyl ester with LiAlD 4 to furnish the respective (5‐ 2 H)‐1‐hexenes. Subsequent olefin metathesis and reduction of the double bond furnished the title compounds. The optical purity of ( R , R )‐ and ( S , S )‐(2,9‐ 2 H 2 )‐ n ‐decane could not be determined by chromatography or polarimetry. Therefore, ( R , R )‐ and ( R , S )‐(5‐ 2 H)‐3‐hydroxy‐2‐hexanone were prepared from their respective hexenes by Wacker oxidation, followed by enantioselective α‐hydroxylation. The enantiopurity could then be determined by NMR spectroscopy because the stereospecifically deuterated hydroxyketones showed separated signals for the subterminal carbon atom (C‐5) in the 13 C NMR spectrum.