Research output: Contribution to journal › Article › peer-review
Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Tandem Cycloaddition of Azides to 3,3-Diaminoacrylonitriles (2-Cyanoacetamidines) and Cornforth-Type Rearrangement as an Approach to 5-Amino-1,2,3-triazole-4-N-substituted Imidamides
AU - Silaichev, Pavel S.
AU - Beryozkina, Tetyana V.
AU - Ilkin, Vladimir
AU - Novikov, Mikhail S.
AU - Dehaen, Wim
AU - Bakulev, Vasiliy A.
N1 - We gratefully acknowledge financial support of this work by the Russian Science Foundation (18-13-00161).
PY - 2023/7/7
Y1 - 2023/7/7
N2 - An efficient base-catalyzed, metal-free method for thesynthesisof 5-amino-1,2,3-triazole-4-N-sulfonyl- and arylimidamides,directed by the structure of the amidine group, has been developed.It is based on a previously unknown tandem process involving cycloadditionreaction to 3,3-diaminoacrylonitriles (2-cyanoacetamidines) with aryl(alkyl)sulfonylor aryl azides and Cornforth-type rearrangement. During the reactionoptimization, different factors were found to facilitate the titlereaction, which include the use of a strong base and N-mono- or N,N & PRIME;-disubstituted3,3-diaminoacrylonitriles. The reaction is tolerant to variously N-monosubstituted and N,N & PRIME;-disubstituted 3,3-diaminoacrylonitriles and to various aryl-and aryl/alkyl sulfonyl azides. The developed method has a broad scopeand can be applied to obtain a variety of 5-amino-1,2,3-triazole-4-carbimidamidesbearing at the N-1 position alkyl, allyl, propargyl, benzyl,cycloalkyl, and heteroaryl substituents and sulfonyl and aryl substituentsat the amidine group. Post-cyclization reactions of prepared 5-amino-1,2,3-triazoleswith DMF-DMA DMA-DMF leads to 1,2,3-triazolo[4,5-d]pyrimidines, 8-aza purine analogues demonstrating the applicabilityof the prepared compounds in organic synthesis.
AB - An efficient base-catalyzed, metal-free method for thesynthesisof 5-amino-1,2,3-triazole-4-N-sulfonyl- and arylimidamides,directed by the structure of the amidine group, has been developed.It is based on a previously unknown tandem process involving cycloadditionreaction to 3,3-diaminoacrylonitriles (2-cyanoacetamidines) with aryl(alkyl)sulfonylor aryl azides and Cornforth-type rearrangement. During the reactionoptimization, different factors were found to facilitate the titlereaction, which include the use of a strong base and N-mono- or N,N & PRIME;-disubstituted3,3-diaminoacrylonitriles. The reaction is tolerant to variously N-monosubstituted and N,N & PRIME;-disubstituted 3,3-diaminoacrylonitriles and to various aryl-and aryl/alkyl sulfonyl azides. The developed method has a broad scopeand can be applied to obtain a variety of 5-amino-1,2,3-triazole-4-carbimidamidesbearing at the N-1 position alkyl, allyl, propargyl, benzyl,cycloalkyl, and heteroaryl substituents and sulfonyl and aryl substituentsat the amidine group. Post-cyclization reactions of prepared 5-amino-1,2,3-triazoleswith DMF-DMA DMA-DMF leads to 1,2,3-triazolo[4,5-d]pyrimidines, 8-aza purine analogues demonstrating the applicabilityof the prepared compounds in organic synthesis.
UR - https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=tsmetrics&SrcApp=tsm_test&DestApp=WOS_CPL&DestLinkType=FullRecord&KeyUT=001013699100001
UR - http://www.scopus.com/inward/record.url?partnerID=8YFLogxK&scp=85156090251
U2 - 10.1021/acs.joc.3c00151
DO - 10.1021/acs.joc.3c00151
M3 - Article
VL - 88
SP - 8163
EP - 8174
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 13
ER -
ID: 41604326