ISSN:
0009-2940
Keywords:
Selenium
;
Fluorine
;
Amides
;
Cleavage reactions
;
Cycloadditions
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Bis(trifluoromethylketiminoalkyl)diselanes [SeC(=NR)CF3]2 (6) [R = Me (a), iPr (b), tBu (c)] have been prepared in high yields (55-70%) by reaction of the diselane (SeC2F5)2 (2) with RNH2. However, the analogous reaction of 2 with secondary amines, R2NH, results in the cleavage of the Se-Se bond and leads to the N,N-dialkyl-2,2,2-trifluoroselenoacetamides Se=C(NR2)CF3 (7) [R = Me (a), iPr (b)]. Cleavage of 6a-6c with Me3SnH affords the selenoamides Se=C(NHR)CF3 (9) and the corresponding stannylselanes Me3SnSeC(=NR)CF3 (10) [R = Me(a), iPr (b), tBu (c)]. Selenoamides 7 and 9 can also be prepared from pentafluoroethylselenol HSeC2F5 (3), Se=C(F)CF3, (1) or its polymer [SeC(F)CF3]n (4) and primary or secondary amines. N,N-dialkyl-2-methyl-3-fluoro-4,4,4-trifluoroselenoacrylamides Se=C(NR2)C(Me)=C(F)CF3[R = Et (13a), iPr (13b)] are prepared in moderate yields under mild conditions by treating either trifluoromethylselenocarbonyl fluoride (1) or its polymer [SeC(F)CF3]n with 1-dialkylamino-1-propynes. The reaction proceeds by [2 + 2] cycloaddition and stereospecific electrocyclic ring-opening, yielding, with respect to the resulting C=C double bond, the E isomer as the only product. The molecular structures of 7b, 9a and 13b show the typical features of selenoamides with C(Se)-N bond shortening and C-Se bond elongation due to π interaction of the N lone pair with the C=Se double bond. The observed perpendicular orientation of the selenoamide and the alkene units of 13b prevents π delocalization.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19971300717
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