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Intramolecular C–H Amination Reaction Provides Direct Access to 1,2‐Disubstituted Diamondoids
Author(s) -
Hrdina Radim,
Metz Fabian M.,
Larrosa Marta,
Berndt JanPhilipp,
Zhygadlo Yevgeniya Y.,
Becker Sabine,
Becker Jonathan
Publication year - 2015
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.201500691
Subject(s) - chemistry , moiety , intramolecular force , diamondoid , reductive amination , combinatorial chemistry , amination , regioselectivity , adamantane , nitrene , alcohol , cyanation , stereochemistry , organic chemistry , catalysis , molecule
We present a new approach to disubstituted diamondoids from corresponding carboxylic acids. A dirhodium‐acetate‐catalyzed (1 mol‐%) nitrene insertion reaction of sulfamides was, for the first time, applied to intramolecular C–H functionalization reactions of rigid tricyclic frameworks. This straightforward approach enables the effective and regioselective synthesis of a variety of diamondoid‐based cyclic sulfamidates, which are synthetically valuable building blocks. Reductive deprotection of the sulfamidate moiety leads to corresponding 1,3‐amino alcohol derivatives. Oxidation of the sulfamidate moiety by KMnO 4 provides access to 1,3‐keto alcohols or imines. Finally, we report the synthesis of Vildagliptin ® analogues as new antidiabetic drug candidates (DPP‐4 inhibitors).