Nontadpole contribution to the mass splitting (m K — m π )

Pd‐catalyzed desulfitative Hiyama coupling with sulfonyl chlorides

“…To our delight, the mixture displayed an obvious effect to the cross-coupling reaction (69-75%) ( Table 1, entries 9-11) and solvent consisting of DMF and CH 3 CN (volume ratio 1:1) was shown to be best ( Table 1, entry 12). Finally, we adjusted the constitution of DMF and CH 3 CN in the range of 9:1 to 1:9 ( Table 1, entries [13][14][15][16][17][18][19][20]. A volume ratio of 1:4 (DMF vs. CH 3 CN) was chosen for the following optimization ( Table 1, entry 19).…”

“…The first job using arylsulfonyl chlorides as reagents in Pd-catalyzed Heck-type cross-coupling reactions was reported by Kasahara and Miura. [3][4][5][6] Development came to a standstill for more than 10 years until Vogel's series of achievement were published from 2003. [7] Arylsulfonyl chlorides have been demonstrated as a class of electrophilic reagents in Pd-catalyzed desulfitative C-C cross-coupling reactions since then.…”

“…[7] Arylsulfonyl chlorides have been demonstrated as a class of electrophilic reagents in Pd-catalyzed desulfitative C-C cross-coupling reactions since then. Many types of coupling reaction, such as Negishi, [8] Stille, [9][10][11] Suzuki, [12] Heck, [13] Sonogashira, [14][15][16] homocoupling [17,18] and carbonylation [19] have been well developed. However, it has not been extended to Pd-catalyzed C-C bond formation with organosilanes (Hiyama cross-coupling; Fig.…”

A Theoretical Probe of Mechanistic Trichotomy in RhIII‐Catalyzed Annulation with Alkyne MIDA Boronates: Roles of Salt, Solvent, and Coupling Partner

“…The 3-isoquinolone boron reagent [15] has seldom been utilized in syntheses up to now, even though the two skeletons are undoubtedly important in natural products and pharmaceutical agents. Recently, Glorius and co-workers [16] reported that 3-isoquinolone MIDA boronates can efficiently be constructed by employing N-(pivaloyloxy)benzamide (1a) and alkyne MIDA boronates under Rh III catalysis conditions (Scheme 1, Table 1), and the product formed can be used in the Suzuki-Miyaura reaction with high efficiency.…”

Palladium‐Catalyzed Desulfitative Sonogashira–Hagihara Cross‐Couplings of Arenesulfonyl Chlorides and Terminal Alkynes

“…[15] Arene-and alkanesulfonyl chlorides are readily available compounds, but have rarely been used as coupling partners in transition metal-catalyzed cross-coupling reactions with organometallic species to construct carbon-carbon bonds. Arenesulfonyl chlorides have been engaged in carbon-vinylation, [16] carbon-carbonylation, [17] and homo-couplings. [18] Recently, we have disclosed the palladium-catalyzed Stille, carbonylative Stille, [19] Suzuki-Miyaura [20] and Heck-Mizoroki [21] desulfitative cross-coupling reactions with sulfonyl chlorides.…”