53691-60-4Relevant articles and documents
DTBB-catalyzed lithiation of 4-hetero-substituted dibenzothiins
Yus, Miguel,Foubelo, Francisco,Ferrandez, Jose V.
, p. 726 - 727 (2002)
The DTBB-catalyzed lithiation of 4-hetero-substituted dibenzothiins (phenoxathiin, phenothiazine, and thianthrene) gives the corresponding functionalized organolithium intermediates, which by reaction with different electrophiles afford the expected funct
Dibenzothiepins, phthalans and phthalides from 4-heterosubstituted dibenzothiins
Yus, Miguel,Foubelo, Francisco,Ferrández, José V.
, p. 2083 - 2092 (2007/10/03)
The lithiation of 4-heterosubstituted dibenzothiins 1 (phenoxathiin, phenothiazine and thianthrene) with lithium and a catalytic amount of 4,4′-di-tert-butylbiphenyl (DTBB, 7.5% molar) in THF at temperatures ranging from -90 to -78°C gives the corresponding functionalised organolithium intermediate I, which by reaction with different electrophiles [H2O, D2O, ButCHO, PhCHO, Ph(CH2)2CHO, Me2CO, Et2CO, (CH2)5CO, (CH2)7CO] at the same temperature, followed by hydrolysis, gives the expected functionalised thiols 2. Cyclisation of some thiols 2 under acidic conditions leads to the corresponding seven-membered dibenzo heterocycles 5. In the case of thianthrene 1c, after addition of a carbonyl compound as the first electrophile [MeCHO, ButCHO, Me2CO, Et2CO, (CH2)5CO], the corresponding intermediate II can be lithiated again and react with a second electrophile. Diols 3 are obtained after hydrolysis when a carbonyl compound [ButCHO, PhCHO, Ph(CH2)2CHO, Me2CO, Et2CO, (CH2)5CO] is used as the second electrophile. Acidic cyclisation of diols 3 gives substituted phthalans 6 in almost quantitative yields. Finally, in the case of using carbon dioxide as the second electrophile, phthalides 4 are obtained after acidic hydrolysis.
