Recent Developments in Enantioselective Metal‐Catalyzed Domino Reactions

This review updates the major progress in the field of enantioselective one‐, two‐, and multi‐component domino reactions promoted by chiral metal catalysts, covering the literature since the beginning of 2012. It illustrates how enantioselective metal‐catalyzed processes have emerged as outstanding tools for the development of a wide variety of fascinating one‐pot asymmetric domino reactions, allowing complex and diverse structures to be easily generated from simple materials in a single step. During the last 4 years, a myriad of already existing as well as completely novel and powerful asymmetric domino processes have been developed on the basis of asymmetric metal catalysis, taking economical advantages, such as avoiding costly protecting groups and time‐consuming purification procedures after each step. Abbreviations: acac: acetylacetonate; Ad: 1‐adamantyl; Ar: aryl; BArF: tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate; BBN: 9‐borabicyclo[3.3.1]nonane; BINAP: 2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl; BINAP(O): 2‐diphenylphosphino‐2′‐diphenylphosphinyl‐1,1′‐binaphthalene; BINOL: 1,1′‐bi‐2‐naphthol; BIPHEP: 2,2′‐bis(diphenylphosphino)‐1,1′‐biphenyl; Bipy: bipyridine; Bn: benzyl; Boc: tert ‐butoxycarbonyl; bod: bicyclo[2.2.2]octane‐2,5‐diene; Box: bisoxazoline; bpe: 1,2‐bis(2‐pyridyl)ethane; Bs: p ‐bromobenzenesulfonyl (brosyl); Bz: benzoyl; Cat: catalyst; Cbz: benzyloxycarbonyl; CMOF: chiral mixed metal‐organic framework; cod: cyclooctadiene; coe: cyclooctene; Cp: cyclopentadienyl; CPME: cyclopentyl methyl ether; Cy: cyclohexyl; DABCO: 1,4‐diazabicyclo[2.2.2]octane; dba: ( E,E )‐dibenzylideneacetone; DBDMH: 1,3‐dibromo‐5,5‐dimethylhydantoin; DCE: dichloroethane; de : diastereomeric excess; Dec: decyl; DET: diethyl tartrate; DIPEA: diisopropylethylamine; DME: 1,2‐dimethoxyethane; DMF: N,N‐ dimethylformamide; DTBM: di‐ tert ‐butylmethoxy; ee : enantiomeric excess; EWG: electron‐withdrawing group; Fesulphos: 1‐phosphino‐2‐sulfenylferrocene; Hept: heptyl; Hex: hexyl; HFIPA: hexafluoroisopropyl alcohol; HMPA: hexamethylphosphoramide; JohnPhos: (2‐biphenyl)di‐ tert ‐butylphosphine; Josiphos: 1‐[2‐(diphenylphosphino)ferrocenyl]ethyldicyclohexylphosphine ethanol adduct; L: ligand; Mandyphos: 1,1′‐bis[(dimethylamino)benzyl]‐2,2′‐bis(diphenylphosphino)ferrocene; Me‐DuPhos: 1,2‐bis(2,5‐dimethylphospholano)benzene; MOM: methoxymethyl; Ms: mesyl; MS: molecular sieves; MTBE: methyl tert‐ butyl ether; Naph: naphthyl; NBS: N‐ bromosuccinimide; Ns: nosyl (4‐nitrobenzenesulfonyl); Oct: octyl; Pent: pentyl; Phos: phosphinyl; Phox: phosphinooxazoline; Pin: pinacolato; PG: protecting group; Phth: phthalimido; Piv: pivaloyl; PMB: p ‐methoxybenzyl; PMP: 1,2,2,6,6‐pentamethylpiperidine; PTAD: 4‐phenyl‐1,2,4‐triazoline‐3,5‐dione; Py: pyridyl; Pybox: 2,6‐bis(2‐oxazolyl)pyridine; QUINOX: (quinolin‐2‐yl)‐oxazoline; rs : regioselectivity ratio; r.t.: room temperature; SDS: sodium dodecyl sulfate; Segphos: 5,5′‐bis(diphenylphosphino)‐4,4′‐bi‐1,3‐benzodioxole; SES: β‐trimethylsilylethanesulfonyl; Taniaphos: [2‐diphenylphosphinoferrocenyl]( N , N ‐dimethylamino)(2‐diphenylphosphinophenyl)methane; TBS: tert ‐butyldimethylsilyl; TEA: trimethylamine; Tf: trifluoromethanesulfonyl; TFA: trifluoroacetic acid; THF: tetrahydrofuran; TIPS: triisopropylsilyl; TMG: 1,1,3,3‐tetramethylguanidine; TMS: trimethylsilyl; Tol: tolyl; Ts: 4‐toluenesulfonyl (tosyl); VANOL: 3,3′‐diphenyl‐2,2′‐bi‐1‐naphthol; Walphos: 1‐{2‐[2′‐(diphenylphosphino)phenyl]ferrocenyl}ethyldi[3,5‐bis(trifluoromethyl)phenyl]phosphine; Xyl: 3,5‐dimethylphenyl. magnified image