Organic Letters
Letter
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(18) Borylation of 1k using the [RhCl(cod)]2/CsF system (Table 1,
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(22) Oxidative addition of thioanisole derivatives to the Rh(I) complex
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(23) ipso-Borylation of 1a was significantly inhibited when the reaction
was performed in the presence of radical scavengers such as 2,2,6,6-
tetramethylpiperidine 1-oxyl (TEMPO) or a Galvinoxyl free radical
(Table S6). These results suggested involvement of a one-electron
transfer mechanism for C−S bond cleavage, although further
mechanistic studies are required.
(24) Although electron-rich thioanisoles were also borylated by this
method, a possibility that the ipso-borylation proceeded via the
mechanism based on SNAr-type reaction could not be excluded.
(25) For the detection of borylrhodium(I) species by ESI-MS analysis,
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(26) A variety of organothiorhodium(I) bis(phosphine) complexes
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(27) Rh-catalyzed borylation of a mixture of 1b (0.1 mmol) and 1e (0.1
mmol) with 2a (0.1 mmol) at 80 °C for 30 min afforded 3b (1.7% GC
yield) and 3e (51% GC yield), respectively. This result indicated that
this borylation reaction favors electron-deficient thioarenes and
supports that C−S bond cleavage is the rate-determining step. See the
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(30) Ir-catalyzed C−H borylation of 6a afforded the desired meta-
borylated product in 37% yield, and a large amount of 6a was recovered.
(13) For recent examples, see: (a) Yokoyama, Y.; Unoh, Y.; Hirano, K.;
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(14) For recent examples of removable directing groups used in the C−
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(15) For selected examples of Rh-catalyzed C−S bond cleavage, see:
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