Recent Catalytic Asymmetric Syntheses of 3,3‐Disubstituted Indolin‐2‐ones and 2,2‐Disubstituted Indolin‐3‐ones

Abstract Disubstituted oxindoles represent an important family of bioactive compounds and synthetic derivatives that mimic natural products. The construction of the asymmetric quaternary carbon at C‐3 or C‐2 is therefore a challenging problem for organic chemists. In the last years, many papers have appeared on asymmetric catalytic methods for the synthesis of these compounds, in particular about spirocyclic derivatives and this literature has been largely reviewed, as well as the literature on 3‐substituted‐3‐hydroxyoxindoles and 3‐substituted‐3‐aminooxindoles. On the other hand, the literature on non‐spirocyclic 3,3‐dialkyloxindoles as well as on 2,2‐disubstituted 3‐indolinones has not fully reviewed since our previous review on this topic. This review aims to fill this gap covering the literature on these topics. Abbreviations : Alloc=allyloxycarbonyl; Ant=anthracenyl; BINOL=1,1′‐binaphthalene‐2,2′‐diol; Boc= t ‐butoxycarbonyl; Bz=benzoyl; Cbz=benzyloxycarbonyl; CSA=camphorsulfonic acid; Cy=cyclohexyl; DABCO=1,4‐diazabicyclo[2.2.2]octane; dba=bis(dibenzylideneacetone); DBU=1,8‐diazabicyclo[5.4.0]undec‐7‐ene; DDQ=2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone; (DHQD) 2 AQN=hydroquinidine (anthraquinone‐1,4‐diyl) diether; (DHQD) 2 PHAL=hydroquinidine 1,4‐phthalazinediyl diether; (DHQD) 2 PYR=hydroquinidine 2,5‐diphenyl‐4,6‐pyrimidinediyl diether; DIPEA= N , N ‐diisopropylethylamine; esp=α,α,α′,α′‐tetramethyl‐1,3‐benzenedipropionic acid; HFIP=1,1,1,3,3,3‐hexafluoro‐2‐propanol; HMDS=hexamethyldisilazane; β‐ICD=β‐isocupreidine; LG=leaving group; Mes=2,4,6‐trimethylphenyl; Moc=methoxycarbonyl; MOM=methoxymethyl; MS=molecular sieves; MsOH=methanesulfonic acid; NHC=N‐heterocyclic carbene; Npt=naphthyl; PG=protecting group; Phg=phenylglycine; Phth=phthalimidyl; Piv=2,2‐dimethylpropanoyl; PMB=4‐methoxybenzyl; Red‐Al=sodium bis(2‐methoxyethoxy)aluminium hydride; Suc=succinimidyl; TBDPS= tert ‐butyldiphenylsilyl; TBS= tert ‐butyldimethylsilyl; TES=triethylsilyl; TIPS=triisopropylsilyl; TMEDA= N , N , N′,N′ ‐tetramethylethylenediamine; TMG=1,1,3,3‐tetramethylguanidine; TMS=trimethylsilyl; Ts=4‐toluenesulfonyl. magnified image