Observation of a Stable Carbocation in a Consecutive Criegee Rearrangement with Trifluoroperacetic Acid

2000 ◽  
Vol 65 (13) ◽  
pp. 3926-3933 ◽  
Author(s):  
Pavel A. Krasutsky ◽  
Igor V. Kolomitsyn ◽  
Paul Kiprof ◽  
Robert M. Carlson ◽  
Andrey A. Fokin
Keyword(s):  
Trifluoroperacetic Acid

On the synthesis of 3,4-dihydroxyprolines. II. Synthesis, stereochemistry and reactivity of some 3,4-Epoxy-DL-proline derivatives

1975 ◽  
Vol 28 (11) ◽  
pp. 2479 ◽  
Author(s):  
CB Hudson ◽  
AV Robertson ◽  
WRJ Simpson
Keyword(s):  
Acid Hydrolysis ◽  
Methyl Esters ◽  
High Yield ◽  
Butyl Esters ◽  
Epoxy Acids ◽  
Trifluoroperacetic Acid ◽  
Catalytic Hydrogenolysis ◽  
Direct Separation ◽  
Proline Derivatives ◽  
Hydrolysis Of

N-Protected esters of 3,4-dehydro-DL-proline react with trifluoroperacetic acid to give, in high yield, approximately equal amounts of the corresponding stereoisomeric 3,4-epoxy-DL-proline derivatives, direct separation of which proved difficult. However individual members of the two families were obtained by discovery of selective transformations and fractionations. Relative configurations of the two 3,4-epoxy-N-tosylproline methyl esters were established by borohydride reduction to authentic 4-hydroxy-N-tosylprolinols. Epoxide reduction is regioselective. Extensive p.m.r. analyses then permitted stereochemical assignment of other derivatives. These epoxides are remarkably resistant to catalytic hydrogenolysis, and to hydration in acid or alkali. N-Substituted 3,4-epoxyproline methyl esters undergo ready β-elimination in alkali to yield the corresponding 4-hydroxy-2,3- dehydroproline esters and ultimately the N-substituted pyrrole-2- carboxylic acid or ester. Prolonged aqueous acid hydrolysis of 3,4- epoxy-N-tosylprolines, or of their methyl esters, gives mixtures of 3,4-dihydroxy-N-tosyl-DL-prolines in the 2,3-cis-3,4-trans and 2,3- trans-3,4-trans families. Their stereochemistry was allotted from p.m.r. of the diacetate methyl esters. During acid hydrolysis of 3,4- epoxy-N-tosylproline methyl esters, the ester of the trans stereoisomer hydrolyses selectively, and some epimerization of the cis stereoisomer occurs. Ester hydrolysis is much faster than epoxide hydration. Anhydrous acid cleavage of 3,4-epoxy-N-tosyl-DL-proline t-butyl esters to the epoxy acids is unusually slow.

ChemInform Abstract: KINETICS OF REACTION OF TRIFLUOROPERACETIC ACID WITH NAPHTHALENE

1976 ◽  
Vol 7 (16) ◽  
pp. no-no
Author(s):  
A. A. AKHREM ◽  
P. A. KISELEV ◽  
D. I. METELITSA
Keyword(s):  
Trifluoroperacetic Acid ◽  
Kinetics Of Reaction ◽  
Kinetics Of

Trifluoroperacetic Acid

2001 ◽  
Author(s):  
Kenneth C. Caster ◽  
A. Somasekar Rao ◽  
H. Rama Mohan
Keyword(s):  
Trifluoroperacetic Acid

The oxidation of aromatic amines by trifluoroperacetic acid

1962 ◽  
Vol 11 (3) ◽  
pp. 475-475
Author(s):  
L. I. Khmel'nitskii ◽  
T. S. Novikova ◽  
S. S. Novikov
Keyword(s):  
Aromatic Amines ◽  
Trifluoroperacetic Acid

Stepwise Photoreduction of (iso)Alloxazine N-Oxides in the Presence of 1,4-Cyclohexadiene

1974 ◽  
Vol 29 (7-8) ◽  
pp. 549-551 ◽  
Author(s):  
Monika Gladys ◽  
Wolfgang-R. Knappe
Keyword(s):  
Direct Synthesis ◽  
Trifluoroperacetic Acid

The direct synthesis of (iso)alloxazine N-oxides using trifluoroperacetic acid in situ is reinvestigated, showing sensitivity towards steric (peri) hindrance. The photoreduction of these N-oxides in the presence of 1,4-cyclohexadiene yields the parent (iso)alloxazine. The reduction of the N-oxides by initially formed dihydro (iso)alloxazine is ruled out for the photoreduction.

Trifluoroperacetic Acid in Consecutive Criegee Rearrangement and Carboxonium Ions Generation

ChemInform ◽  
2005 ◽  
Vol 36 (38) ◽  
Author(s):  
Pavel A. Krasutsky ◽  
Igor V. Kolomitsyn
Keyword(s):  
Trifluoroperacetic Acid

Interaction of 3-β-chloro-Δ5-steroids with trifluoroperacetic acid

1999 ◽  
Vol 35 (1) ◽  
pp. 75-79
Author(s):  
N. V. Kovganko ◽  
D. V. Drozdov ◽  
S. K. Ananich
Keyword(s):  
Trifluoroperacetic Acid
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