The Golden Age of Transfer Hydrogenation

ConspectusChiral alcohols are important building blocks in the pharmaceutical and fine chemical industries. The enantioselective reduction of prochiral ketones catalyzed by transition metal complexes, especially asymmetric transfer hydrogenation (ATH) and asymmetric hydrogenation (AH), is one of the most efficient and practical methods for producing chiral alcohols. In both academic laboratories and industrial operations, catalysts based on noble metals such as ruthenium, rhodium, and iridium dominated the asymmetric reduction of ketones. However, the limited availability, high price, and toxicity of these critical metals demand their replacement with abundant, nonprecious, and biocommon metals. In this respect, the reactions catalyzed by first-row transition metals, which are more abundant and benign, have attracted more and more attention.As one of the most abundant metals on earth, iron is inexpensive, environmentally benign, and of low toxicity, and as such it is a fascinating alternative to the preci...

Iron-, Cobalt-, and Nickel-Catalyzed Asymmetric Transfer Hydrogenation and Asymmetric Hydrogenation of Ketones

The organometallic approach is one of the most active topics in catalysis. The application of NH functionality in organometallic catalysis has become an important and attractive concept in catalyst design. NH moieties in the modifiers of organometallic ca

The N-H functional group in organometallic catalysis.

Asymmetric hydrosilylation, transfer hydrogenation and hydrogenation of ketones catalyzed by iridium complexes

While tremendous advances have been made in asymmetric synthesis, the resolution of racemates is still the most important industrial approach to the synthesis of chiral compounds. The use of enzymes for the kinetic resolution (KR) of racemic substrates to afford enantiopure compounds in high enantioselectivity and good yield has long been a popular strategy in synthesis. However, transition metal-mediated and more recently organocatalyzed KRs have gained popularity within the synthetic community over the last two decades due to the progress made in the development of chiral catalysts for asymmetric reactions. Many catalytic non-enzymatic procedures have been developed providing high enantioselectivity and yield for both products and recovered starting materials. Indeed, the non-enzymatic KR of racemic compounds based on the use of a chiral catalyst is presently an area of great importance in asymmetric organic synthesis. The goal of this review is to provide an update on the principal developments of catalytic non-enzymatic KR covering the literature since 2004. This review is subdivided into seven sections, according to the different types of compounds that have been resolved through catalytic non-enzymatic KR, such as alcohols, epoxides, amines, alkenes, carbonyl derivatives, sulfur compounds and ferrocenes.



Abbreviations: Ac: acetyl; acac: acetylacetone; AQN: anthraquinone; Ar: aryl; Atm: atmosphere; BINAM: 1,1′-binaphthalenyl-2,2′-diamine; BINAP: 2,2′-bis(diphenylphosphanyl)-1,1′-binaphthyl; BINEPINE: phenylbinaphthophosphepine; BINOL: 1,1′-bi-2-naphthol; Bmim: 1-butyl-3-methylimidazolium; Bn: benzyl; Boc: tert-butoxycarbonyl; Box: bisoxazoline; BSA: bis(trimethylsilyl)acetamide; Bu: butyl; Bz: benzoyl; c: cyclo; CBS: Corey–Bakshi–Shibata; Cbz: benzyloxycarbonyl; COD: cyclooctadiene; COE: cyclooctene; Cy: cyclohexyl; Dba: (E,E)-dibenzylideneacetone; DBU: 1,8-diazabicyclo[5.4.0]undec-7-ene; DCC: N,N′-dicyclohexylcarbodiimide; de: diastereomeric excess; DEAD: diethyl azodicarboxylate; Dec: decanyl; DHQD: dihydroquinidine; Difluorphos: 5,5′-bis(diphenylphosphino)-2,2,2′,2′-tetrafluoro-4,4′-bi-1,3-benzodioxole; DIPEA: diisopropylethylamine: DKR: dynamic kinetic resolution; DMAP: 4-dimethylaminopyridine; DMSO: dimethyl sulfoxide; DNA: deoxyribonucleic acid; DOSP: N-(dodecylbenzenesulfonyl)prolinate; DTBM: di-tert-butylmethoxy; ee: enantiomeric excess; Et: ethyl; equiv.: equivalent; Fu: furyl; Hex: hexyl; HIV: human immunodeficiency virus; HMDS: hexamethyldisilazide; KR: kinetic resolution; L: ligand; LDA: lithium diisopropylamide; MAO: methylaluminoxane; Me: methyl; Ms: mesyl; MTBE: methyl tert-butyl ether; Naph: naphthyl; nbd: norbornadiene; NBS: N-bromosuccinimide; NIS: N-iodosuccinimide; Pent: pentyl; Ph: phenyl; Piv: pivaloyl; PMB: p-methoxybenzoyl; Pr: propyl Py: pyridyl; r.t.: room temperature; s: selectivity factor; Segphos: 5,5′-bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole; (S,S′,R,R′)-Tangphos: (1S,1S′,2R,2R′)-1,1′-di-tert-butyl-(2,2′)-diphospholane; TBS: tert-butyldimethylsilyl; TBDPS: tert-butyldiphenylsilyl; TCCA: trichloroisocyanuric acid ; TEA: triethylamine; TEMPO: tetramethylpentahydropyridine oxide; THF: tetrahydrofuran; Thio: thiophene; Tf: trifluoromethanesulfonyl; TMS: trimethylsilyl; Tol: tolyl; Ts: 4-toluenesulfonyl (tosyl)

Catalytic Non-Enzymatic Kinetic Resolution

The interaction of 1,3-bis(2-formylphenoxy)-2-propanol with chiral 1,2-diaminocyclohexane gave novel chiral macrocyclic ONNO-type ligands which were fully characterized by IR, NMR, MS and CD. The catalyst systems generated in situ from the chiral cyclic ONNO ligands and the iridium hydride complex [IrHCl 2 (COD)] 2 have been used for the first time in the asymmetric transfer hydrogenation of aromatic ketones using 2-propanol as a source of hydrogen, giving the corresponding optically active alcohols with high chemical yields and good to excellent enantioselectivities (up to 92% ee). The reactions can be performed in air and the catalytic experiments are greatly simplified.

Synthesis of novel chiral macrocyclic ONNO-type ligands and use in asymmetric transfer hydrogenation

Kinetic resolution of racemic secondary alcohols catalyzed by chiral diaminodiphosphine-Ir(I) complexes.

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Synthesis of novel chiral macrocyclic ONNO-type ligands and use in asymmetric transfer hydrogenation

Kinetic resolution of racemic secondary alcohols catalyzed by chiral diaminodiphosphine-Ir(I) complexes.