The Toxicity of Vesicants and Some Other Compounds to the Pyruvate Oxidase System* (Brain)

shown by GLC analysis and 13C NMR to contain 5a (lo%), unknown compounds (12%), and 3a (78%). The data (GLC and '3c NMR) are identical with those from the products from reaction of 1 with methanol a t room temperature. Acknowledgment. We acknowledge grants from the Research Committee of the New Zealand Universities J. Org. Chem. 1990,55, 4144-4153 Grants Committee and helpful discussions with Professor M. A. Battiste.Supplementary Material Available: 13C and 'H NMR spectra for compounds 1,3a-d, 5a,b, 6a,b, 12,14a-c, 16a,b, and 18a,b (26 pages). Ordering information is given on any current masthead page.The carbenoid intermediate derived by treating ethyl 2-diazo-4-phthalimidobutyrate with rhodium(I1) octanoate undergoes transannular cyclization onto the adjacent imido carbonyl group. The resulting cyclic carbonyl ylide dipole was trapped with several dipolarophiles. In an attempt to prepare related substrates for cyclization studies, the reaction of ethyl lithiodiazoacetate with various aldehydes and ketones was studied. Treatment of the a-diazo-0-hydroxy ester derived from acetone or cyclopentanone with rhodium(I1) octanoate gave rise to a 0-keto ester. The exclusive phenyl shift encountered with acetophenone is in keeping with migration to an electron-deficient center. The reaction works well with acrolein, leading to high yields of 3-oxo-4-pentenoate. The 1,2-hydrogen shift pathway was found to proceed much faster than intramolecular cyclopropanation. Dehydration of the a-diazo-@-hydroxy esters generates vinyl diazo esters, which readily cyclize to lH-pyrazoles on thermolysis.

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“…1980,102, 6161. (13) Ratcliff, R. W.; Saltzmann, T. N.; Christensen, B. G. Tetrahedron Lett. 1980, 21, 31.…”

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confidence: 99%

Reaction of carbonyl compounds with ethyl lithiodiazoacetate. Studies dealing with the rhodium(II)-catalyzed behavior of the resulting adducts

Padwa¹,

Kulkarni²,

Zhang³

1990

J. Org. Chem.

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Inhibitors of Enzymes Containing Thiol Groups and Toxicity

Peters¹

1963

Biochemical Lesions and Lethal Synthesis

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An Investigation of the Relationship Between the Sulfhydryl Activity and the Toxicity of a Series of Vinyl Sulfone Molluscicidal Agents

Rocca¹,

Thomas²

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The Toxicity of Vesicants and Some Other Compounds to the Pyruvate Oxidase System* (Brain)

Cited by 3 publications

References 33 publications

Reaction of carbonyl compounds with ethyl lithiodiazoacetate. Studies dealing with the rhodium(II)-catalyzed behavior of the resulting adducts

Reaction of carbonyl compounds with ethyl lithiodiazoacetate. Studies dealing with the rhodium(II)-catalyzed behavior of the resulting adducts

Inhibitors of Enzymes Containing Thiol Groups and Toxicity

An Investigation of the Relationship Between the Sulfhydryl Activity and the Toxicity of a Series of Vinyl Sulfone Molluscicidal Agents

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