Synthesis of 4-alkyl-2-iodosobenzoic acids: potent catalysts for the hydrolysis of phosphorus esters

Panetta, Charles A.; Garlick, Stephanie M.; Durst, H. D.; Longo, Frederick R.; Ward, Joseph P.

doi:10.1021/jo00305a011

Cited by 34 publications

(39 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Firstly, N-(4-tert-butyl-2-iodophenyl)methyl)imidazole has been prepared by reacting imidazole (102 mg, 1.5 mmol) with, successively, NaH (90 mg, 60% in mineral oil, 2.2 mmol) and 4-tert-butyl-2-iodobenzyl methanesulfonate (810 mg, 2.2 mmol, obtained from the corresponding alcohol, [31] mesyl chloride and Et 3 N) in DMF (6 mL) at room temperature. The reaction mixture was stirred overnight at room temperature, diluted with water and extracted with dichloromethane.…”

Section: Synthesis Of the (Nhc)pt(0)a C H T U N G T R E N N U N G (Dvmentioning

confidence: 99%

Cyclometalated N‐Heterocyclic Carbene‐Platinum Catalysts for the Enantioselective Cycloisomerization of Nitrogen‐Tethered 1,6‐Enynes

et al. 2011

View full text Add to dashboard Cite

Platinum(II) complexes which combine six-membered N-heterocyclic carbene-containing metallacyclic units and monodentate chiral phosphines have been prepared. The key step of their synthesis is the intramolecular oxidative addition of N-2-iodobenzylimidazolylidene-platinum (0) ]heptenes has been established by X-ray diffraction studies. The method has been extended then to the cycloisomerization of dienynes with enantiotopic vinyl groups. An (S)-phenyl-Binepine-platinum(II) complex allows total diastereoselectivity and high enantioselectivity levels to be attained in these reactions (ees up to 95%) which represent the first enantioselective desymetrizations achieved via enyne cycloisomerizations.

show abstract

Section: Synthesis Of the (Nhc)pt(0)a C H T U N G T R E N N U N G (Dvmentioning

confidence: 99%

Cyclometalated N‐Heterocyclic Carbene‐Platinum Catalysts for the Enantioselective Cycloisomerization of Nitrogen‐Tethered 1,6‐Enynes

et al. 2011

View full text Add to dashboard Cite

show abstract

“…An effective reagent in the first regard is o-iodosobenzoic acid, [12][13][14]19,22,50 while aqueous perhydroxide ion has shown promise for the latter. 21 Yang et al 21 have demonstrated that aqueous perhydroxide ion reacts with VX 40 times faster than aqueous hydroxide ion.…”

Section: Introductionmentioning

confidence: 99%

Molecular orbital calculations on the P?S bond cleavage step in the hydroperoxidolysis of nerve agent VX

Patterson

Cramer

1998

J. Phys. Org. Chem.

View full text Add to dashboard Cite

The P-S bond cleavage process in the hydroperoxidolysis of a model system for the nerve agent VX was studied using ab initio and semiempirical molecular orbital methods. Aqueous solvation effects were included through single-point calculations using the semiempirical SM5.2PD/A continuum solvation model and geometries optimized at the HF/MIDI! level of theory. The predominant pathway for P-S bond cleavage involves pseudorotation of a low-energy trigonal bipyramidal intermediate followed by apical ligand ejection. In aqueous solution, the free energy barriers for these processes are found to be 14.3 and 4.6 kcal mol À1 , respectively, with electronic energies calculated at the MP2/cc-pVDZ//HF/MIDI! level of theory. By comparison with another continuum model of solvation (PCM), it is concluded that the SM5.2PD/A model performs well even for hypervalent phosphorus species, in spite of not having included any such molecules in the model's parameterization set.

show abstract

“…Thus, in 1990, Panetta et al reported the separate isolation of the iodoxolone and iodoso valence tautomers of 4-propyl-as well as 4-pentyl-2-iodosobenzoic acids. 7 These extraordinary results have been reiterated in a recent authoritative review, 3b so that it becomes imperative to verify them, particularly because of the importance of IBA and its analogues as decontamination agents for toxic phosphonates and phosphates. 4b,c, [5][6][7][8] We have now reinvestigated the case of the 4-pentyl 'tautomers' (3a and 3b), and report here that the previously described 7 compounds were misassigned; in fact, only a single 4-pentyl-2-iodosobenzoic acid can be isolated, and it is best represented as the 'closed' iodoxolone compound, 3a.…”

mentioning

confidence: 99%

The ‘valence tautomers’ of o-iodosobenzoic acid: the case of 4-pentyl-2-iodosobenzoic acid

Moss¹,

Emge²

1998

Chem. Commun.

View full text Add to dashboard Cite

Synthesis of 4-alkyl-2-iodosobenzoic acids: potent catalysts for the hydrolysis of phosphorus esters

Cited by 34 publications

References 0 publications

Cyclometalated N‐Heterocyclic Carbene‐Platinum Catalysts for the Enantioselective Cycloisomerization of Nitrogen‐Tethered 1,6‐Enynes

Cyclometalated N‐Heterocyclic Carbene‐Platinum Catalysts for the Enantioselective Cycloisomerization of Nitrogen‐Tethered 1,6‐Enynes

Molecular orbital calculations on the P?S bond cleavage step in the hydroperoxidolysis of nerve agent VX

The ‘valence tautomers’ of o-iodosobenzoic acid: the case of 4-pentyl-2-iodosobenzoic acid

Contact Info

Product

Resources

About