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Z ‐Selective Hydrothiolation of Racemic 1,3‐Disubstituted Allenes: An Atom‐Economic Rhodium‐Catalyzed Dynamic Kinetic Resolution
Author(s) -
Pritzius Adrian B.,
Breit Bernhard
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201507623
Subject(s) - kinetic resolution , desymmetrization , chemistry , allylic rearrangement , rhodium , ligand (biochemistry) , catalysis , denticity , medicinal chemistry , enantioselective synthesis , combinatorial chemistry , organic chemistry , crystal structure , biochemistry , receptor
A Z ‐selective rhodium‐catalyzed hydrothiolation of 1,3‐disubstituted allenes and subsequent oxidation towards the corresponding allylic sulfones is described. Using the bidentate 1,4‐bis(diphenylphosphino)butane (dppb) ligand, Z/E ‐selectivities up to >99:1 were obtained. The highly atom‐economic desymmetrization reaction tolerates functionalized aromatic and aliphatic thiols. Additionally, a variety of symmetric internal allenes, as well as unsymmetrically disubstituted substrates were well tolerated, thus resulting in high regioselectivities. Starting from chiral but racemic 1,3‐disubstituted allenes a dynamic kinetic resolution (DKR) could be achieved by applying ( S , S )‐Me‐DuPhos as the chiral ligand. The desired Z ‐allylic sulfones were obtained in high yields and enantioselectivities up to 96 % ee .