A Novel Triphosphoramidite Ligand for Highly Regioselective Linear Hydroformylation of Terminal and Internal Olefins

The first triphosphorus ligand has been designed and synthesized for highly regioselective linear hydroformylations. A very high <i><i>l</i></i>/<i><i>b</i></i> ratio (up to 471, 99.8% linear selectivity) was obtained in the linear hydroformylation of representative terminal and internal olefins. For the range of substrates tested, the regioselectivities achieved utilizing the novel triphosphoramidite ligand were much better than those of the bisphosphoramidite ligand and close to those of the tetraphosphoramidite ligand

Rh/Wudaphos-Catalyzed Asymmetric Hydrogenation of Sodium α‑Arylethenylsulfonates: A Method To Access Chiral α‑Arylethylsulfonic Acids

A highly enantioselective hydrogenation of various sodium α-arylethenylsulfonates catalyzed by Rh/chiral ferrocenyl bisphosphorus ligand (Wudaphos) was successfully developed to construct a series of chiral α-arylethylsulfonic acids in the presence of CF₃SO₃H with full conversion and good to excellent enantioselectivity (>99% conversion, up to 96% ee) under mild reaction conditions for the first time. Moreover, the control experiment results showed that the non-covalent ion pair interaction between the α-arylethenylsulfonic acid and the Wudaphos ligand plays an important role in this asymmetric hydrogenation system

Rh/SPO-WudaPhos-Catalyzed Asymmetric Hydrogenation of α‑Substituted Ethenylphosphonic Acids via Noncovalent Ion-Pair Interaction

Asymmetric hydrogenation of α-substituted ethenylphosphonic acids has been successfully achieved by Rh/ferrocenyl chiral bisphosphorus ligand (SPO-Wudaphos) through noncovalent ion-pair interaction between the substrate and catalyst under mild reaction conditions without base. A series of chiral phosphonic acids were obtained with excellent results (up to 98% ee, >99% conversion, 2000 TON). Moreover, the control experiments showed that the noncovalent ion-pair interaction was critical in this asymmetric hydrogenation

Selective Rhodium-Catalyzed Hydroformylation of Alkynes to α,β-Unsaturated Aldehydes with a Tetraphosphoramidite Ligand

A tetraphosphoramidite ligand was successfully applied to a Rh-catalyzed hydroformylation of various symmetrical and unsymmetrical alkynes to afford corresponding α,β-unsaturated aldehyde products in good to excellent yields (up to 97% yield). Excellent chemo- and regioselectivities and high activities (up to 20 000 TON) were achieved. The corresponding α,β-unsaturated aldehyde products can be transformed into many useful and important organic molecules, such as indenamine derivatives and lukianol pyrroles. This great performance makes the hydroformylation of alkynes highly practical with great potential

Integration of Milstein Ru–PNN and Rh–Tribi/Tetrabi for Isomerization Linear Selective Hydroformylation of Far Internal Alkenes

Converting cheap and abundant internal alkenes to value-added linear aldehydes is of great importance but not an addressed issue. In this paper, an integration of a Milstein-type Ru–PNN catalyst and our Rh–Tribi/Tetrabi catalyst was first demonstrated in highly improved isomerization linear selective hydroformylation of 2-, 3-, and 4-alkenes, yielding excellent linear selectivities and activities (linear selectivity improvements of 2.2–58%, up to 94.2–98.6%, and turnover numbers improvements of 61–335 TON, up to 385–851) compared to the Ru–PNN/Rh–Bisbi system

Highly Enantioselective Synthesis of Chiral Succinimides via Rh/Bisphosphine-Thiourea-Catalyzed Asymmetric Hydrogenation

We have successfully developed a highly enantioselective hydrogenation of various 3-aryl and 3-methyl maleinimides to access enantiomerically pure 3-substituted succinimides catalyzed by Rh/bisphosphine-thiourea (ZhaoPhos). This efficient catalytic system furnished the desired 3-substituted succinimide products with high yields and enantioselectivities (up to 99% yield, full conversions, almost all 3-aryl succinimide products up to 99% ee, and 3-methyl succinimide with 83% ee). Our catalytic system has a strong substrate tolerance and generality. Whether the N-substituted group of maleinimides is H or other protecting groups, the maleinimides were hydrogenated well (up to >99% ee, 99% yield). Moreover, the hydrogenation succinimide products can be readily utilized for the construction of biologically active molecules, such as chiral amides and pyrrolidines

Highly Enantioselective Asymmetric Hydrogenation of Carboxy-Directed α,α-Disubstituted Terminal Olefins via the Ion Pair Noncovalent Interaction

The <i>t</i>-Bu-Wudaphos was successfully applied into Rh-catalyzed asymmetric hydrogenation of α,α-disubstituted terminal olefins bearing a carboxy-directed group with excellent reactivities and enantioselectivities via the ion pair noncovalent interaction (up to >99% conversion, 98% yield, 98% ee) under mild reaction conditions without base. In addition, control experiments were conducted, and the results demonstrated that the ion pair noncovalent interaction between ligand and substrate played an important role in achieving an outstanding performance in this asymmetric hydrogenation

Rhodium/Yanphos-Catalyzed Asymmetric Interrupted Intramolecular Hydroaminomethylation of <i>trans</i>-1,2-Disubstituted Alkenes

The first interrupted asymmetric hydroaminomethylation reaction was developed. The challenging <i>trans</i>-1,2-disubstituted olefins were employed as substrates, and a series of valuable chiral pyrrolidinones and pyrrolidines were obtained in high yields with high regioselectivities and excellent enantioselectivities. Several synthetic transformations were conducted, demonstrating the high synthetic utility of our method. A creative route for the synthesis of vernakalant and Enablex was also developed

Correction to “Rhodium/Yanphos-Catalyzed Asymmetric Interrupted Intramolecular Hydroaminomethylation of <i>trans</i>-1,2-Disubstituted Alkenes”

Correction to “Rhodium/Yanphos-Catalyzed Asymmetric Interrupted Intramolecular Hydroaminomethylation of <i>trans</i>-1,2-Disubstituted Alkenes

Iridium Catalysts with f‑Amphox Ligands: Asymmetric Hydrogenation of Simple Ketones

A series of modular and rich electronic tridentate ferrocene aminophosphoxazoline ligands (f-amphox) have been successfully developed and used in iridium-catalytic asymmetric hydrogenation of simple ketones to afford corresponding enantiomerically enriched alcohols under mild conditions with superb activities and excellent enantioselectivities (up to 1 000 000 TON, almost all products up to >99% ee, full conversion). The resulting chiral alcohols and their derivatives are important intermediates in pharmaceuticals