Abstract
(Chemical Equation Presented) Combined analyses of experimental and computational studies on the Cu-catalyzed three-component reactions of sulfonyl azides, terminal alkynes and amines, alcohols, or water are described. A range of experimental data including product distribution ratio and trapping of key intermediates support the validity of a common pathway in the reaction of 1-alkynes and two distinct types of azides substituted with sulfonyl and aryl(alkyl) groups. The proposal that bimolecular cycloaddition reactions take place initially between triple bonds and sulfonyl azides to give N-sulfonyl triazolyl copper intermediates was verified by a trapping experiment. The main reason for the different outcome from reactions between sulfonyl and aryl(alkyl) azides is attributed to the lability of the N-sulfonyl triazolyl copper intermediates. These species are readily rearranged to another key intermediate, ketenimine, into which various nucleophiles such as amines, alcohols, or water add to afford the three-component coupled products: amidines, imidates, or amides, respectively. In addition, the proposed mechanistic framework is in good agreement with the obtained kinetics and competition studies. A computational study (B3LYP/LACV3P*+) was also performed confirming the proposed mechanistic pathway that the triazolyl copper intermediate plays as a branching point to dictate the product distribution.
| Original language | English |
|---|---|
| Pages (from-to) | 5520-5528 |
| Number of pages | 9 |
| Journal | Journal of Organic Chemistry |
| Volume | 73 |
| Issue number | 14 |
| DOIs | |
| Publication status | Published - 18 Jul 2008 |
| Externally published | Yes |
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ASJC Scopus subject areas
- Organic Chemistry
Cite this
Mechanistic studies on the Cu-catalyzed three-component reactions of sulfonyl azides, 1-alkynes and amines, alcohols, or water : Dichotomy via a common pathway. / Eun, Jeong Yoo; Ahlquist, Mårten; Bae, Imhyuck; Sharpless, K. Barry; Fokin, Valery V.; Chang, Sukbok.
In: Journal of Organic Chemistry, Vol. 73, No. 14, 18.07.2008, p. 5520-5528.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Mechanistic studies on the Cu-catalyzed three-component reactions of sulfonyl azides, 1-alkynes and amines, alcohols, or water
T2 - Dichotomy via a common pathway
AU - Eun, Jeong Yoo
AU - Ahlquist, Mårten
AU - Bae, Imhyuck
AU - Sharpless, K. Barry
AU - Fokin, Valery V.
AU - Chang, Sukbok
PY - 2008/7/18
Y1 - 2008/7/18
N2 - (Chemical Equation Presented) Combined analyses of experimental and computational studies on the Cu-catalyzed three-component reactions of sulfonyl azides, terminal alkynes and amines, alcohols, or water are described. A range of experimental data including product distribution ratio and trapping of key intermediates support the validity of a common pathway in the reaction of 1-alkynes and two distinct types of azides substituted with sulfonyl and aryl(alkyl) groups. The proposal that bimolecular cycloaddition reactions take place initially between triple bonds and sulfonyl azides to give N-sulfonyl triazolyl copper intermediates was verified by a trapping experiment. The main reason for the different outcome from reactions between sulfonyl and aryl(alkyl) azides is attributed to the lability of the N-sulfonyl triazolyl copper intermediates. These species are readily rearranged to another key intermediate, ketenimine, into which various nucleophiles such as amines, alcohols, or water add to afford the three-component coupled products: amidines, imidates, or amides, respectively. In addition, the proposed mechanistic framework is in good agreement with the obtained kinetics and competition studies. A computational study (B3LYP/LACV3P*+) was also performed confirming the proposed mechanistic pathway that the triazolyl copper intermediate plays as a branching point to dictate the product distribution.
AB - (Chemical Equation Presented) Combined analyses of experimental and computational studies on the Cu-catalyzed three-component reactions of sulfonyl azides, terminal alkynes and amines, alcohols, or water are described. A range of experimental data including product distribution ratio and trapping of key intermediates support the validity of a common pathway in the reaction of 1-alkynes and two distinct types of azides substituted with sulfonyl and aryl(alkyl) groups. The proposal that bimolecular cycloaddition reactions take place initially between triple bonds and sulfonyl azides to give N-sulfonyl triazolyl copper intermediates was verified by a trapping experiment. The main reason for the different outcome from reactions between sulfonyl and aryl(alkyl) azides is attributed to the lability of the N-sulfonyl triazolyl copper intermediates. These species are readily rearranged to another key intermediate, ketenimine, into which various nucleophiles such as amines, alcohols, or water add to afford the three-component coupled products: amidines, imidates, or amides, respectively. In addition, the proposed mechanistic framework is in good agreement with the obtained kinetics and competition studies. A computational study (B3LYP/LACV3P*+) was also performed confirming the proposed mechanistic pathway that the triazolyl copper intermediate plays as a branching point to dictate the product distribution.
UR - http://www.scopus.com/inward/record.url?scp=48249116347&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=48249116347&partnerID=8YFLogxK
U2 - 10.1021/jo800733p
DO - 10.1021/jo800733p
M3 - Article
C2 - 18557650
AN - SCOPUS:48249116347
VL - 73
SP - 5520
EP - 5528
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 14
ER -