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Keywords = hypervalent bromine

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8 pages, 804 KB  
Article
Anion Transfer Reactions from Chiral Hypervalent Iodine Macrocycles
by Mina Dumre Pandey, Tahir Awais, Krishna Pandey, Samsul Arafin, Eli Jones and Kyle N. Plunkett
Organics 2025, 6(4), 52; https://doi.org/10.3390/org6040052 - 20 Nov 2025
Viewed by 906
Abstract
The direct chlorination, bromination and azidation of beta keto esters, 2-acetyl-1-tetralone and methyl 1-oxo-2,3-dihydro-1H-indene-2-carboxylate is achieved utilizing anion-coordinated hypervalent iodine benziodazoles derived from hypervalent iodine macrocycles. This reaction, which introduces the halogen, azido or cyano group at the alpha carbon atom of beta [...] Read more.
The direct chlorination, bromination and azidation of beta keto esters, 2-acetyl-1-tetralone and methyl 1-oxo-2,3-dihydro-1H-indene-2-carboxylate is achieved utilizing anion-coordinated hypervalent iodine benziodazoles derived from hypervalent iodine macrocycles. This reaction, which introduces the halogen, azido or cyano group at the alpha carbon atom of beta keto esters, is accomplished in chloroform at 60 °C and results in the formation of a chiral center. Depending on the structure of the benziodazole reagent, the reaction can have mild enantioselectivity. The reaction between 2-acetyl-1-tetralone and phenylalanine-derived hypervalent iodine benziodazoles results in the chlorinated product with 26% enantiomeric excess. Full article
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18 pages, 4732 KB  
Article
Chiral Bromonium Salt (Hypervalent Bromine(III)) with N-Nitrosamine as a Halogen-Bonding Bifunctional Catalyst
by Yasushi Yoshida, Tatsuya Ao, Takashi Mino and Masami Sakamoto
Molecules 2023, 28(1), 384; https://doi.org/10.3390/molecules28010384 - 2 Jan 2023
Cited by 15 | Viewed by 3667
Abstract
There has been a great focus on halogen-bonding as a unique interaction between electron-deficient halogen atoms with Lewis basic moieties. Although the application of halogen-bonded atoms in organic chemistry has been eagerly researched in these decades, the development of chiral molecules with halogen-bonding [...] Read more.
There has been a great focus on halogen-bonding as a unique interaction between electron-deficient halogen atoms with Lewis basic moieties. Although the application of halogen-bonded atoms in organic chemistry has been eagerly researched in these decades, the development of chiral molecules with halogen-bonding functionalities and their utilization in asymmetric catalysis are still in the\ir infancy. We have previously developed chiral halonium salts with amide functionalities, which behaved as excellent catalysts albeit in only two reactions due to the lack of substrate activation abilities. In this manuscript, we have developed chiral halonium salts with an N-nitrosamine moiety and applied them to the Mannich reaction of isatin-derived ketimines with malonic esters. The study focused on our novel bromonium salt catalyst which provided the corresponding products in high yields with up to 80% ee. DFT calculations of the chiral catalyst structure suggested that the high asymmetric induction abilities of this catalyst are due to the Lewis basic role of the N-nitrosamine part. To the best of our knowledge, this is the first catalytic application of N-nitrosamines. Full article
(This article belongs to the Special Issue Recent Advances in Stereoselective Catalytic Reactions)
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