Synthesis of Biphenyls Mimicking the Structure of the Antimitotic Rhazinilam

Palladium‐Catalyzed Intramolecular C(sp3)H Functionalization: Catalyst Development and Synthetic Applications

“…The residue was purified by flash chromatography (silica gel, heptanes/ethyl acetate 95:5) to afford 1 a as a colorless oil (1.42 g, 92 %). [26] 10.4, 28.6, 52.4, 118.7, 122.6, 127.7, 129.4, 131.2, 131.9, 136.1 ppm.…”

The Palladium‐Catalyzed C–H Activation of Benzylic gem‐Dialkyl Groups

“…In most other cases 1 d, which probably arises from desilylation and dehydrogenation of the resulting primary alcohol, was formed in negligible quantities. The influence of the base was then assessed (entries [8][9][10][11]). Among the bases tested, K 2 CO 3 (entry 8) and K 3 PO 4 (entry 9) gave the highest yields of 1 b and the highest 1 b:1 c ratio.…”

“…[8] These were obtained in few steps from commercially available iodo-or bromobenzenes according to procedures described in our previous reports. [9] First, the influence of the benzylic R substituent and of the halogen X was studied (entries 1-8). As shown with iodides 1 a, 2 a, 3 a, and 4 a, substrates with relatively large R groups gave higher yields of olefin than those with smaller groups.…”

The Directed Ortho Metallation (DoM)–Cross‐Coupling Nexus. Synthetic Methodology for the Formation of Aryl–Aryl and Aryl–Heteroatom–Aryl Bonds

“…In the search for mimics of the antimitotic alkaloid, rhazinilam 98 (Scheme 14.22), a DoM-Migita-Stille cross-coupling tactic was pursued [134]. Thus, metallation of the benzodioxene 91 followed by stannylation affords 92, which, upon the Migita-Stille cross-coupling with the 2-halo-N-Boc-aniline 93, gives derivatives 94 in modest to good yields.…”