2023
DOI: 10.26434/chemrxiv-2023-dmfqh
|View full text |Cite
Preprint
|
Sign up to set email alerts
|

Spectroscopic and Computational Study of Organocatalytic Umpolung of Bromocations: An Accelerated Stereoselective Dibromination Protocol

Abstract: Herein, the reversal of polarity of cationic bromine, organocatalytically, is presented. NBS, a proven bromocation source was converted to a superior bromoanion reagent by H/Br exchange with a secondary amine, substantiated with spectroscopic and computational evidences. The concept has further been used in a successful accelerated organocatalyzed dibromination of olefins, in a non-hazardous, commercially viable process with a wide substrate scope. The reactivity of key entities has been observed through NMR k… Show more

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
1
1

Citation Types

0
2
0

Year Published

2023
2023
2024
2024

Publication Types

Select...
1
1

Relationship

1
1

Authors

Journals

citations
Cited by 2 publications
(2 citation statements)
references
References 11 publications
0
2
0
Order By: Relevance
“…various reactivity patterns were observed with different types of substrates towards the dibromination protocol: NBS-300 mol%, pyrrolidine-10 mol% (Figure 1). 18 The olefinic bond of substituted methyl (E)-cinnamates and β-nitrostyrenes reacted well with the established protocol whereas, substituted β-methyl-β-nitrostyrenes surprisingly did not provide the corresponding dibromo product except for 4-methoxy-β-methyl β-nitrostyrene. Thus a detailed investigation was carried out to find the reactivity pattern of C⚌C functionality in β-methylβ-nitrostyrenes in comparison to substituted methyl (E)-cinnamates and β-nitrostyrenes.…”
Section: Resultsmentioning
confidence: 82%
“…various reactivity patterns were observed with different types of substrates towards the dibromination protocol: NBS-300 mol%, pyrrolidine-10 mol% (Figure 1). 18 The olefinic bond of substituted methyl (E)-cinnamates and β-nitrostyrenes reacted well with the established protocol whereas, substituted β-methyl-β-nitrostyrenes surprisingly did not provide the corresponding dibromo product except for 4-methoxy-β-methyl β-nitrostyrene. Thus a detailed investigation was carried out to find the reactivity pattern of C⚌C functionality in β-methylβ-nitrostyrenes in comparison to substituted methyl (E)-cinnamates and β-nitrostyrenes.…”
Section: Resultsmentioning
confidence: 82%
“…Furthermore, the above protocol can be extended Chemistry-A European Journal to the asymmetric dibromination reaction [29] employing chiral organocatalysts and/or a chiral bromocation source, which is currently underway in our laboratory. [30] Experimental Section General procedure for the dibromination of olefins: To a stirred solution of NÀ bromosuccinimide (1, 300 mol %) in dry dioxane, in an amber colored vial, were added olefin (6, 100 mol %) and pyrrolidine (2 e, 50 mol %) sequentially. The reaction mixture was stirred at rt and the reaction progress was monitored by TLC.…”
Section: Discussionmentioning
confidence: 99%