Corrigendum to: A General Catalytic Hydroamidation of 1,3-Dienes: Atom-Efficient Synthesis of N -Allyl Heterocycles, Amides, and Sulfonamides (Angewandte Chemie International Edition, (2014), 53, 6, (1630-1635), 10.1002/anie.201308874)

Debasis Banerjee, Kathrin Junge, Matthias Beller

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Abstract

Careful repetition of the catalytic procedure described in this Communication revealed the formation of further isomers. In addition to the reported 1,4-addition product A, which is formed as major compound, the reaction yields small amounts (<5%) of the 1,2-addition product (D), as well as minor amounts (10–20%) of the two isomers B and C (Figure). Figure (Figure presented.) Structure of major product A and regioisomers B, C, and D. Based on these findings the yields of the substrate scope presented in Table, and Scheme of the original manuscript are corrected in the following. The authors regret that the structure of product (3 g) shown in Table, entry 7, was not correct. Repetition of the experiment and detailed analysis revealed that for this special substrate mono- (10 g, mixture of isomers) and double (11 g) allylation takes place on the methylene carbon and not on nitrogen of the amide moiety. Additionally, the structure of the commercial substrate 2 k was corrected (Table, entry 11). Here, allylation of the amine group occurs yielding 74% of 12 k. The reactions of the bicyclic amide 2 e (Table, entry 5), amide 2 h (Table, entry 8) and the sulfonamide 2 j (Table, entry 10) were repeated several times yielding no product. Intermolecular hydroamidation of 1 a with N-heterocycles, amides, and sulfonamides.[a] (Table presented.) [a] General reaction conditions: 1 a (4 mmol), 2 (1 mmol), Pd catalyst (2.5 mol %), L7 (5 mol %), Na2CO3 (0.5 mmol), toluene (3 mL), 140 °C, 20 h. [b] Yields of the isolated mixture of regioisomers A, B, C, and D. The ratio of formed isomers was detected by NMR and is presented in the Supporting Information. [c] 120 °C, 10 h. [d] L10 (5 mol %), Na2CO3 (1 mmol), n-heptane (5 mL). Table shows the reaction of phthalimides 2 a and 2 b with different 1,3-dienes as well as 2- and 4-vinylpyridine using the optimized catalytic system. In case of reaction of 2,3-dimethylbutadiene (1 e), 1,3-cyclohexadiene (1 i) and 2-vinylpyridine (1 j) one single product (1,4-addition) was formed in 45–91% yields. Reactions of methyl 2,4-pentadienoate (1 g) and methyl sorbate (1 h) with phthalimide 2 a (Table, entries 6 and 7) and 4-vinylpyridine (1 k) with phthalimide 2 b (Table, entry 11) were not reproducible. Palladium-catalyzed hydroamidation of dienes and vinyl arenes with 2 a and 2 b.[a] (Table presented.) [a] General reaction conditions: 1 (1 mmol), 2 (1 mmol), Pd catalyst (2.5 mol %), L7 (5 mol %), Na2CO3 (0.5 mmol), toluene (3 mL), 140 °C, 20 h. [b] Yields of the isolated mixture of regioisomers A, B, C, and D. The ratio of formed isomers was detected by NMR and is presented in the Supporting Information. [c] Catalyst (7.5 mol %), L7 (15 mol %), Na2CO3 (1.5 mmol) used. [d] 3.0 equiv diene and Na2CO3 (1 mmol) used. The reaction of isoprene (1 a) with diclazuril (2 n) provided 4 bA as major regioisomer (Scheme). In a similar manner, thymidine and uridine derivatives were converted into the N-allylated thymidine (4 cA) and uridine derivatives (4 dA). Finally, the reaction of isoprene (1 a) with 6-chloro-1-methyluracil (2 m) was repeated four times yielding no desired product. Scheme (Figure presented.) Pd-catalyzed intermolecular hydroamidation of uracil, diclazuril, thymidine, and uridine derivatives is presented. Yields of the isolated mixture of regioisomers A, B, and C are given. The ratio of isomers was detected by NMR (see the Supporting Information). All catalytic experiments were repeated at least twice to ensure reproducibility. The corrected analytical data and spectra of products are given in the revised Supporting Information published along with this Corrigendum. The authors apologize for these mistakes. The authors thank Prof. Giovanni Poli at Sorbonne Universités, Institut Parisien de Chimie Moléculaire, for pointing out the mistake regarding the structure of 3 g. This notice made the careful revision possible. The authors thank Bianca Wendt and Dr. Wolfgang Baumann for repeating the experiments and providing the data for this corrigendum.

Original languageEnglish
Pages (from-to)16436-16438
Number of pages3
JournalAngewandte Chemie International Edition in English
Volume56
Issue number52
DOIs
StatePublished - 22 Dec 2017
Externally publishedYes

Keywords

  • 1,3-dienes
  • amides
  • hydroamidation
  • palladium catalysis
  • sulfonamides

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