2022
DOI: 10.1021/acs.orglett.2c03206
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Direct Minisci-Type C–H Amidation of Purine Bases

Abstract: A method for the C–H carboxyamidation of purines has been developed that is capable of directly installing primary, secondary, and tertiary amides. Previous Minisci-type investigations on purines were limited to alkylations and arylations. Herein, we present the first method for the direct C–H amidation of a wide range of purines: xanthine, guanine, and adenine structures, including guanosine- and adenosine-type nucleosides. The Minisci-type reaction is also metal-free, cheap, operationally simple, scalable, a… Show more

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Cited by 16 publications
(7 citation statements)
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“…The radical B undergoes a single‐electron transfer (SET) to form the nitrogen‐centered cation C , which gives the product 3 aa after deprotonation (path a). Alternatively, the product 3 aa can be furnished from B via the H radical abstraction by SO 4 ⋅ − (path b) [9d,h] …”
Section: Resultsmentioning
confidence: 99%
See 1 more Smart Citation
“…The radical B undergoes a single‐electron transfer (SET) to form the nitrogen‐centered cation C , which gives the product 3 aa after deprotonation (path a). Alternatively, the product 3 aa can be furnished from B via the H radical abstraction by SO 4 ⋅ − (path b) [9d,h] …”
Section: Resultsmentioning
confidence: 99%
“…Initially, the homolytic cleavage of the peroxydisulfate dianion forms sulfate anion radical SO 4 ⋅ − [19] . Then, the reaction of radical SO 4 ⋅ − with 2‐oxo‐2‐(phenylamino)acetic acid 2 a generates a carbamoyl radical A through hydrogen atom transfer (HAT) and decarboxylation processes [9d,h,20] . Next, the selective addition of the carbamoyl radical A to the C6‐position of azauracil 1 a produces the nitrogen‐centered radical B .…”
Section: Resultsmentioning
confidence: 99%
“…Rather than using Kochi conditions, however, we set out to develop a metal- and light-free Giese method (conditions B), inspired by our recent success with metal- and light-free Minisci reactions. 18 Using DMSO as the solvent allows for the breakdown of S 2 O 8 2− V to the active SO 4 −· VI ( E ox = +2.51–3.1 V vs. SHE) 19 under mild conditions (40–50 °C), without the need for metal mediation or photolysis (Scheme 2). 18,20 This could potentially be exploited in the Giese reaction, since SET between VI and carboxylate I ( E ox = +1.17 V vs. SCE) 17,21 can then occur to give radical VII , 22 which should decarboxylate to give the carbamoyl radical II 9 a ,23 for the Giese addition with 8 .…”
Section: Resultsmentioning
confidence: 99%
“…18 Using DMSO as the solvent allows for the breakdown of S 2 O 8 2− V to the active SO 4 −· VI ( E ox = +2.51–3.1 V vs. SHE) 19 under mild conditions (40–50 °C), without the need for metal mediation or photolysis (Scheme 2). 18,20 This could potentially be exploited in the Giese reaction, since SET between VI and carboxylate I ( E ox = +1.17 V vs. SCE) 17,21 can then occur to give radical VII , 22 which should decarboxylate to give the carbamoyl radical II 9 a ,23 for the Giese addition with 8 . Unlike conditions A, radical III would presumably undergo hydrogen atom transfer (HAT) instead of SET/protonation to yield 9 , due to the absence of an obvious reductant.…”
Section: Resultsmentioning
confidence: 99%
“…Carbamoyl radicals add efficiently to a wide range of unsaturated systems, including alkenes, 1 alkynes, 2 arenes 3 and heteroarenes (Minisci reaction), 4 allowing the straightforward incorporation of the amide functional group onto carbon skeletons (Fig. 1A).…”
mentioning
confidence: 99%