Reaction of indium ate complexes with allylic compounds. Controlling SN2/SN2′ selectivity by solvents

Deprotonative Metalation of Functionalized Aromatics Using Mixed Lithium–Cadmium, Lithium–Indium, and Lithium–Zinc Species

“…[17] Even if not associated in the form of a zincate, the combination behaves synergically, allowing efficient and chemoselective deprotonation reactions. To seek more efficient and direct methods for introducing functionalities into aromatic rings including het-erocycles, we focused on the deprotonative metalation using the corresponding mixtures with cadmium [18] and indium [19] instead of zinc to investigate the effect of a different size of metal ion.…”

Chemo‐ and Regioselective C(sp3)H Arylation of Unactivated Allylarenes by Deprotonative Cross‐Coupling

“…It is noteworthy that excellent regioselectivity is observed in the substrates in Table 3, even when the steric and electronic parameters of the allylbenzene starting materials are varied 10. 12…”

“…10 We envisioned that a strong base could divert the chemoselectivity from olefin coordination and insertion of allylbenzene in the Heck coupling to transmetalation of the metalated allyl (Scheme , left) 11. 12 The catalyst/ligand combination would control the regioselectivity of the arylation in the DCCP, thus enabling the formation of α‐arylated products that are inaccessible by the Heck pathway. It is noteworthy that this approach is distinct from known CH activation/arylations of allylbenzenes and related substrates 13…”

Chemo‐ and Regioselective C(sp3)H Arylation of Unactivated Allylarenes by Deprotonative Cross‐Coupling

“…It is noteworthy that excellent regioselectivity is observed in the substrates in Table 3, even when the steric and electronic parameters of the allylbenzene starting materials are varied. [10,12] When the DCCP with TBS protected bromoindole (3 j) was scaled to 1 mmol with a ratio of 4:5:1 of 1 a:2:3 j in the presence of 5 mol % Pd(OAc) 2 and 20 mol % PCy 3 , the product 4 j was isolated in 77 % yield (Scheme 4).…”

“…[9, 10] We envisioned that a strong base could divert the chemoselectivity from olefin coordination and insertion of allylbenzene in the Heck coupling to transmetallation of the metallated allyl (Scheme 1, left). [11, 12] The catalyst/ligand combination would control the regioselectivity of the arylation in the DCCP, thus enabling the formation of α-arylated products that are inaccessible via the Heck pathway. It is noteworthy that this approach is distinct from known C–H activation/arylations of allylbenzenes and related substrates.…”