2024-03-29T05:45:02Z
https://nagoya.repo.nii.ac.jp/oai
oai:nagoya.repo.nii.ac.jp:00024552
2023-01-16T05:03:43Z
1903:1904:1905
Brønsted Acid/Silane Catalytic System for Intramolecular Hydroalkoxylation and Hydroamination of Unactivated Alkynes
Shibuya, Masatoshi
Fujita, Shoji
Abe, Masanori
Yamamoto, Yoshihiko
open access
“This document is the Accepted Manuscript version of a Published Work that appeared in final form in [ACS Catalysis], copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see [http://pubs.acs.org/articlesonrequest/AOR-ccnW7GCz94tz5qnyYxff].”
alkyne
Brønsted acid
electrophilic activation
hydroalkoxylation
hydroamination
The Brønsted acid-catalyzed intramolecular hydroalkoxylation and hydroamination of unactivated alkynes are described. We found that unactivated alkynes are electrophilically activated by a catalytic amount of bis(trifluoromethanesulfonyl)imide to undergo intramolecular hydroalkoxylation and hydroamination. In the presence of silane, the formed reactive exo-cyclic enol ether and exo-cyclic enamine intermediates are effectively reduced to the corresponding saturated cyclic ethers and N-protected cyclic amines. The 2,4-cis and 2,5-cis pyrrolidine derivatives are produced with high diastereoselectivity. Taking advantage of this selectivity, the 2,5-cis-disubstituted prolinol was also synthesized from glutamic acid in the optically active form.
ACS Publications
2017-04-07
eng
journal article
AM
http://hdl.handle.net/2237/26769
https://nagoya.repo.nii.ac.jp/records/24552
https://doi.org/10.1021/acscatal.7b00403
2155-5435
ACS Catalysis
7
4
2848
2852
https://nagoya.repo.nii.ac.jp/record/24552/files/ACS_catalysis_shibuya_rev2.pdf
application/pdf
991.3 kB
2018-04-07