- Manipulating the Click Reactivity of Dibenzoazacyclooctynes: From Azide Click Component to Caged Acylation Reagent by Silver Catalysis
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Strain-promoted azide–alkyne cycloaddition using dibenzoazacyclooctyne (DBCO) is widely applied in copper-free bioorthogonal reactions. Reported here is the efficient acid-promoted rearrangement and silver-catalyzed amidation of DBCO, which alters its click reactivity robustly. In the switched click reaction, DBCO, as a caged acylation reagent, enables rapid peptide/protein modification after decaging facilitated by silver catalysts, rendering site-specific conjugation of an IgG antibody by a Fc-targeting peptide.
- Ao, Jiwei,Huang, He,Huang, Wei,Jiang, Bofeng,Liu, Junjie,Ren, Xuelian,Shi, Wei,Tang, Feng,Tang, Yubo,Yang, Weibo,Yu, Qun
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supporting information
p. 19940 - 19944
(2020/09/02)
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- Scalable synthesis of strained cyclooctyne derivatives
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Modifications to the Popik synthesis of aza-dibenzocyclooctyne (DIBAC) derivatives are described, which avoids tedious purifications and dramatically improves the yield. A new and analogous route to biarylazacyclooctynone (BARAC) through an amide disconnection was also attempted. The BARAC derivatives prepared were found to be unstable under the conditions employed, undergoing a known rearrangement. Finally, the synthesis of a difluoro-DIBAC derivative with a second-order rate constant intermediate between DIBAC and BARAC derivatives (0.50 M-1) is described. While more difficult to synthesize, this molecule was found to be considerably more stable than any BARAC derivatives that were prepared. Georg Thieme Verlag Stuttgart New York.
- Chadwick, Ryan C.,Van Gyzen, Sabrina,Liogier, Sophie,Adronov, Alex
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p. 669 - 677
(2014/03/21)
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- Iron-catalyzed C-H and C-C bond cleavage: A direct approach to amides from simple hydrocarbons
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Something functional: The title reaction proceeds in the presence of azide and water to deliver amides in high yields, and it can be used in a ring-expansion strategy to generate lactams. A mechanism is proposed based on experimental results. This reaction offers a new approach to functionalizing simple and readily available hydrocarbons. DDQ=2,3-dichloro-5,6-dicyano-1,4- benzoquinone. Copyright
- Qin, Chong,Zhou, Wang,Chen, Feng,Ou, Yang,Jiao, Ning
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supporting information; experimental part
p. 12595 - 12599
(2012/01/15)
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