105494-81-3Relevant academic research and scientific papers
Directed ortho-Metalation of Arenesulfonyl Fluorides and Aryl Fluorosulfates
Talko, Alicja,Antoniak, Damian,Barbasiewicz, Micha?
, p. 2278 - 2286 (2019)
Studies on directed ortho -metalation (DoM) of arenesulfonyl fluorides (ArSO 2 F) with in situ electrophile trapping are presented. Under optimized conditions (LDA, THF, -78 °C), a series of model substrates was mono- and difunctionalized with trimethylsilyl chloride in good yields. The synthetic results reveal powerful directing character of the SO 2 F group, being ahead of bromine and methoxy substituents. Under the same metalation conditions, aryl fluorosulfates (ArOSO 2 F) display fragmentation to arynes and migration of the SO 2 F group to the ortho position (anionic thia-Fries rearrangement).
The Synthesis of Ketones via α-Silyl Sulphides
Ager, David J.
, p. 195 - 204 (2007/10/02)
α-Phenylthiosilanes (2) have been prepared by alkylation of the anion (4) derived from the 1-phenylthio-1-trimethylsilylalkane (1).These anions (4) have benn prepared by a variety of methods including, direct deprotonation of (1), displacement of a phenylthio group by lithium naphthalenide addition of an alkyl-lithium to 1-phenylthio-1-trimethylsilylethene (7), and transmetallation of a tributylstannyl moiety.The formation of an alkyl-lithium by reaction of lithium naphthalenide with a phenyl sulphide provided an additional route to (2) from bis(phenylthio)acetals (8).An alternative path to the α-phenylthiosilanes (2) was to reduce the corresponding α-phenylsulphonylsilane (15); these, in turn, being readily available from alkylation or silylation of α-sulphonyl anions.The α-phenylthiosilanes (2) were converted into the O-trimethylsilylphenylthioacetal (18) by the sila-Pummerer rearrangement, although this was complicated by vinyl sulphide (20) formation in certain cases.Subsequent hydrolysis of (18) and (20) gave the ketone (3).
