Enantioselective Synthesis of 2‐Hydroxyalkyl Diarylphosphinates by Ruthenium‐Catalyzed Asymmetric Transfer Hydrogenation

Zhang, Kaili; Yang, Yue; Liu, Huan; Liu, Qixing; Lv, Jiaqi

doi:10.1002/adsc.201900569

Cited by 12 publications

(3 citation statements)

References 57 publications

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“…These results highlight an oil–water interfacial effect that impacts the catalytic selectivity. It was previously found that “on water” effects − and H-shuttle effects caused by the presence of water were reported to improve the reaction rate or alter the reaction selectivity. − However, in our case, the selectivity enhancement should not be attributed to the effects arising from the presence of water molecules because the oil–water biphasic system gave much higher selectivity than the single water system (82.2% vs 71.5%). The presence of a liquid–liquid interface (biphasic system) should be responsible for the catalytic selectivity enhancement (Figure A(c)).…”

Section: Resultscontrasting

confidence: 50%

Highly Selective Catalysis at the Liquid–Liquid Interface Microregion

et al. 2021

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Liquid-liquid interfaces in principle have the potential to regulate the selectivity of chemical reactions because of large polar gradients and highly anisotropic microenvironments, but have not yet been well exploited. Here, we present an oil-water interface-based strategy to boost catalytic selectivity, exempli ed by selective hydrogenation of α,β-unsaturated aldehydes. The key to this success is the spatially controlled assembly of tubular catalyst particles at the narrow inner interfacial layer of Pickering emulsion water droplets in oil. The catalyst particles that are assembled at the inner interfacial layer of water droplets exhibit much higher selectivity to C=O hydrogenation than ones located either at the outer interfacial layer, in the interior of droplets or at the conventionally-called Pickering emulsion interface. 92.0−98.0% selectivity to the thermodynamically and kinetically unfavorable C=O hydrogenation over the C=C hydrogenation was achieved unexpectedly. The assembly strategy reported here and the unprecedented effects of interface-induced catalytic selectivity enhancement open up a liquid-liquid interface engineering route to tune reaction outcome.

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Section: Resultscontrasting

confidence: 50%

Highly Selective Catalysis at the Liquid–Liquid Interface Microregion

et al. 2021

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“…The subsequent asymmetric transfer hydrogenation was carried out at 50 °C for 6 hours under nitrogen atmosphere. To our delight, the nucleophilic substitution and subsequent asymmetric transfer hydrogenation are compatible in a one‐pot process, giving chiral 1‐phenyl‐2‐(2,2,2‐trifluoroethoxy) ethanol ( 3 a ) in 56% yield and 94% ee (entry 1) [26g,h,27d,28] . Next, other chiral ruthenium complexes 4 b – 4 g , rhodium complex 4 h , and iridium complex 4 i were also screened (entries 2–9).…”

Section: Methodsmentioning

confidence: 99%

One‐Pot Construction of Fluorinated Chiral Alcohols via Sequential Substitution/Asymmetric Transfer Hydrogenation of α‐Bromoarylketones and Fluoroalcohols

et al. 2022

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A one-pot synthesis of fluorinated chiral alcohols from α-bromoarylketones and fluoroalcohols is described. The fluorinated ketone intermediates were formed from α-bromoarylketones with fluoroalcohols as nucleophiles and solvents, which were reduced subsequentially by adding a chiral Ru catalyst and a mixture of formic acid and triethyl amines (FA: TEA = 1.1:1) as hydrogen donor to give 27 examples of fluorinated chiral alcohols in 60-93% yields and 85-98% ee values. Notably, K 3 PO 4 acts as a base in nucleophilic substitution and an additive in reductive step to enhance the reactivity and enantioselectivity, which is crucial for constructing compatible conditions for one-pot process. This one-pot process is also applicable to gram-scale synthesis.

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“…12 In 2019, Tang & Pan's group developed an electrochemical cross-dehydrogenation coupling to construct CN double bonds for the synthesis of rutaecarpine alkaloids (Scheme 2b). 13 To continue our interest in ether/O 2 promoted oxidative cleavage, 8 N -heterocyclic synthesis, 14 and green organic synthesis, 15 we report here an intramolecular oxidative dehydrogenative coupling for the construction of dihydroisoquinolino[2,1- a ]quinazolinones, 2-aryl quinazolinones, and analogues promoted by bis(2-methoxyethyl)ether in the presence of molecular oxygen under clean conditions (Scheme 2c).…”

Section: Introductionmentioning

confidence: 99%