Organoiodinane reagents for phosphate cleavage: experimental and computational studies

Reductive Eliminations from λ3-Iodanes: Understanding Selectivity and the Crucial Role of the Hypervalent Bond

“…3-CenterÀ4-electron bond in λ 3 -iodanes 6. found for this and similar reactions support the validity of the Curtin-Hammett principle: the computed barrier height for the dominant product is consistently lower than the one of the alternative product.…”

The Simultaneous In-Situ Generation of Aldehydes and Phosphorus Ylides: A Convenient Multi-Step One-Pot Olefination Protocol

“…Ϫ Bp 88Ϫ92°C/10 Torr (ref. [32] bp 77°C/ 1.10 (t, J ϭ 7. added dropwise to an ylide solution [34] prepared from propyltriphenylphosphonium bromide (9.6 g, 25 mmol) and sodium amide (Z)-3-(tert-Butyldimethylsilyl)oxy-1-iodo-1-propene: (Z)-3-Iodo-2-propen-1-ol [32] (2.6 mL, 4.6 g, 25 mmol), tert-butylchlorodimethyl-(1.1 g, 28 mmol) in diethyl ether (50 mmol). The reaction mixture was allowed to reach 25°C and was worked up as described in the silane (6.0 mL, 5.3 g, 35 mmol), and imidazole (2.4 g, 35 mmol) were dissolved in N,N-dimethylformamide (25 mL) and kept overpreceding paragraph.…”

O‐Nucleophilicity of Hydroxamate Ions for Cleavage of Carboxylate and Phosphate Esters in Cationic Micelles

“…Hydrolysis and nucleophilic reactions of carboxylate and phosphate esters are involved in many biological processes . The nucleophile‐aided hydrolysis is the most preferred reaction for the detoxification organophosphorus toxic compounds . In this regard, many α‐effect nucleophiles such as o‐ iodosylcarboxylate , peroxides , oximates , hypochlorites , and hydroxamates have been investigated alone or as functionalized surfactants.…”

“…The nucleophile‐aided hydrolysis is the most preferred reaction for the detoxification organophosphorus toxic compounds . In this regard, many α‐effect nucleophiles such as o‐ iodosylcarboxylate , peroxides , oximates , hypochlorites , and hydroxamates have been investigated alone or as functionalized surfactants. Considerable research efforts have been focused on the nucleophilic reagents, such as monoperoxyphthalates , 4‐ N , N ‐dialkylaminopyridines , and metallomicelles , hydroxybenzotriazoles and 5‐alkyl‐1 H ‐tetrazoles for the cleavage of esters.…”