- Ligand coupling reactions of 2-pyridyl, 4-pyridyl and 2-pyrimidyl sulfoxides with grignard reagents
-
The ligand coupling reaction was extended to 3-and 4-pyridyl sulfoxides as well as the 2-pyrimidyl moiety with Grignard reagents. It was found that both 4-pyridyl and 2-pyrimidyl sulfoxides nicely underwent the ligand coupling reactions, but 3-pyridyl sulfoxide underwent ligand exchange.
- Oae, Shigeru,Takeda, Takeshi,Uenishi, Junichi,Wakabayashi, Shoji
-
p. 179 - 182
(2007/10/03)
-
- SENSITIVE NATURE OF LIGAND COUPLING AND PSEUDOROTATION TO ELECTRONIC EFFECT OF SUBSTITUENT---LIGAND COUPLING IN THE REACTIONS OF BENZYLIC ARYL SULFOXIDES WITH BENZYLIC GRIGNARD REAGENTS
-
Unlike the reaction of benzylic 2-pyridyl sulfoxides with benzylic Grignard reagents, in the reaction of p-benzenesulfonylphenyl benzylic sulfoxides with benzylic Grignard reagents, benzylic groups bearing an electronwithdrawing group tends to couple with the aryl group preferentially.This change is considered to be due to a slight change of electronic environements which would effect on the ease of pseudorotation of the incipient ?-sulfurane formed during the reaction.
- Wakabayashi, Shoji,Ishida, Masahiro,Takeda, Takashi,Oae, Shigeru
-
p. 4441 - 4444
(2007/10/02)
-
- LIGAND COUPLING THROUGH ?-SULFURANE --- COMPLETE RETENTION OF GEOMETRIC CONFIGURATION OF ALLYLIC AND VINYLIC GROUPS IN THE REACTIONS OF ALLYLIC AND VINYLIC SULFOXIDES WITH GRIGNARD REAGENTS
-
The reaction of p-benzenesulfonylphenyl crotyl sulfoxide with Grignard reagents is considered to proceed via formation of an incipient ?-sulfurane to afford the coupling product, p-benzenesulfonyl-crotylbenzene, in which the geometric configuration of crotyl group was completely preserved.No rearrangement was observed in the coupling reaction of p-benzenesulfonylphenyl α-methylallyl sulfoxide.Such a complete retention of geometric configuration was also found in the reactions of 2-pyridyl and p-benzenesulfonylphenyl styryl sulfoxides with Grignard reagents.
- Oae, Shigeru,Takeda, Takashi,Wakabayashi, Shoji
-
p. 4445 - 4448
(2007/10/02)
-
- OCCURRENCE OF LIGAND COUPLING IN THE REACTIONS OF VARIOUS SULFOXIDES WITH GRIGNARD REAGENTS
-
Ligand coupling reactions take place not only between benzyl and 2-pyridyl groups and two 2-pyridyl groups in the treatment of benzyl, alkyl and aryl 2-pyridyl sulfoxides with Grignard reagents, but also between such groups as p-benzenesulfonylphenyl, 4-pyridyl, 2-quinolyl and 2-pyrimidyl, and the benzyl group.There are cases in which ligand exchange precedes ligand coupling, especially with 2-heteroaryl groups.In addition, even some alkyl groups were found to couple with the 2-pyridyl group.The ease of coupling seems to be associated with the electronegativity of the coupling carbon atom of the ligand, when one compares the 13C NMR chemical shifts.
- Kawai, Tsutomu,Kodera, Yoichi,Furukawa, Naomichi,Oae, Shigeru,Ishida, Masahiro,et al.
-
p. 139 - 148
(2007/10/02)
-