A Divergent Approach to the Diastereoselective Synthesis of 3,3‐Disubstituted Oxindoles from Atropisomeric N‐Aryl Oxindole Derivatives

Abstract

3,3-Disubstituted oxindoles were divergently synthesized by diastereoselective transformations including nucleophilic addition, alkylation, and cycloaddition using common, axially chiral N-aryl oxindoles. Notably, high diastereoselectivities (up to >95:5) were observed with ortho-monosubstituted N-aryl oxindoles to give various oxindole scaffolds, and facile removal of the p-(benzyloxy)aryl moiety in axially twisted amides was achieved by a mild, two-step sequence.

Catalytic Asymmetric Allylic Amination with Isatins, Sulfonamides, Imides, Amines, and N-Heterocycles

“…Liu and co-workers developed a protocol for diastereoselective N -glycosylation of unsaturated hexopyranosides with isatin which gives efficient access to both carbohydrate anomers . Nakazaki described a palladium-catalyzed asymmetric intramolecular arylation procedure that affords axially chiral N -aryl oxindoles and highly enantioselective organocatalytic aza-Michael additions of isatin derivatives to unsaturated diketones were reported by Kanger . Based on the scarcity of catalytic asymmetric C–N bond formations with N -nucleophilic isatins and oxindoles, we decided to investigate the possibility of enantioselective allylic aminations with this important heterocyclic scaffold.…”

Synthesis of Supramolecular A8Bn Miktoarm Star Copolymers by Host‐Guest Complexation

“…The condensation reaction of dicarboxylic acid 9 [13a] with 8 afforded two CTA‐attached G2 products. Four‐CTA‐attached ester G3 was prepared from 10 [20] . The Ullmann coupling reaction of 10 generated tetramethyl ester 11 , which was treated with hydrogen bromide in acetic acid, followed by protection of the two phenolic hydroxyl groups with acetyl groups.…”

“…Four-CTA-attached ester G3 was prepared from 10. [20] The Ullmann coupling reaction of 10 generated tetramethyl ester 11, which was treated with hydrogen bromide in acetic acid, followed by protection of the two phenolic hydroxyl groups with acetyl groups. Afterward, introducing the four CTA units under the condensation conditions with 8 furnished four CTA-attached guest G3.…”

Benzophosphol-3-yl Triflates as Precursors of 1,3-Diarylbenzophosphole Oxides

“…The starting compounds were prepared according to reported methods: phenyl(methyl)phosphine oxide, 36 methyl 2-iodobenzoate, 37 methyl 2-iodo-6-methylbenzoate, 38 methyl 2-iodo-5-chlorobenzoate, 39 2-iodo-4-methoxybenzoic acid, 40 methyl 2-iodo-4-methoxybenzoate, 41 (2-methoxycarbonylphenyl)(methyl)phenylphosphine oxide ( 1a ), 15 [(2-methoxycarbonyl)-6-methylphenyl]methylphenylphosphine oxide ( 1b ), 15 [(2-methoxycarbonyl)-5-chlorophenyl]methylphenylphosphine oxide ( 1c ), 15 [(2-methoxycarbonyl)-4-methoxyphenyl]methylphenylphosphine oxide ( 1d ), 15 1-phenylbenzophospholan-3-one oxide ( 2a ), 15 , 42 1-phenyl-7-methylbenzophospholan-3-one oxide ( 2b ), 15 1-phenyl-6-chlorobenzophospholan-3-one oxide ( 2c ), 15 and 1-phenyl-5-methoxybenzophospholan-3-one oxide ( 2d ). 15 …”