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Synthesis 2021; 53(22): 4221-4230
DOI: 10.1055/a-1638-5783
DOI: 10.1055/a-1638-5783
special topic
Special Issue dedicated to Prof. Sarah Reisman, recipient of the 2019 Dr. Margaret Faul Women in Chemistry Award
Regio- and Stereoselective Addition of Brønsted Acids to Yndiamides: Synthesis of N,O,N- and N,S,N-Trisubstituted Ketene Acetals
S.J.M. thanks the EPSRC Centre for Doctoral Training in Synthesis for Biology and Medicine for studentships (EP/L015838/1), generously supported by AstraZeneca, Diamond Light Source, Defence Science and Technology Laboratory, Evotec, GlaxoSmithKline, Janssen, Novartis, Pfizer, Syngenta, Takeda, UCB and Vertex. E.A.A. thanks the EPSRC for additional support (EP/M019195/1).
Abstract
Yndiamides, N,N-disubstituted alkynes, are versatile building blocks for the synthesis of nitrogen-containing organic molecules. Unlike ynamides, relatives that are inherently polarized by a single nitrogen substituent, their pseudo-symmetric nature renders regioselective reactions challenging. Here we report investigations into the regioselective addition of Brønsted acids to non-symmetric yndiamides, a reaction that delivers N,O,N- and N,S,N-trisubstituted ketene acetals with excellent regio- and stereoselectivity.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1638-5783.
- Supporting Information
Publication History
Received: 17 August 2021
Accepted: 06 September 2021
Accepted Manuscript online:
06 September 2021
Article published online:
21 September 2021
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Low-temperature single-crystal X-ray diffraction data for 3a, 3b, 3c and 7 were collected using a Rigaku Oxford SuperNova diffractometer at 150 K. Raw frame data were reduced using CrysAlisPro and the structures were solved using ‘Superflip’.7a Subsequent refinement was carried out with CRYSTALS.7b Further details on the refinements, including disorder modelling and restraints, are documented in the CIF. CCDC 2103193–2103196 contain the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures.