The use of a new carboranylamidophosphite ligand in the asymmetric Rh-catalyzed hydrogenation of α- and β-dehydroamino acid derivatives

Lyubimov, S. E.; Rastorguev, E. A.; Verbitskaya, T. A.; Petrovskii, P. V.; Hey‐Hawkins, Evamarie; Калинин, В. Н.; Davankov, V. A.

doi:10.1016/j.poly.2011.02.003

Cited by 17 publications

(4 citation statements)

References 36 publications

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“… , The significant improvements in the enantioselectivity and conversion with HFIP compared to methanol (MeOH) and i -PrOH were attributed to its increased acidity and stronger hydrogen-bond donor ability, which, by interrupting the intramolecular hydrogen bond in the substrates, allowed coordination of the chiral catalyst complex and permitted the asymmetric hydrogenation to proceed. A similar Rh-catalyzed asymmetric hydrogenation in HFIP using a chiral carboranylamidophosphite ligand provided high conversions to the desired β-amino acids with modest to good enantioselectivities (46–85% ee) . A related Ni-catalyzed asymmetric hydrogenation of β-boronic α,β-unsaturated esters in the presence of (+)-1,2-bis((2 S ,5 S )-2,5-diphenylphospholano)ethane (( S , S )-Ph-BPE) as the ligand under H 2 atmosphere in HFIP was reported for the synthesis of chiral β-boronic esters with high enantioselectivities .…”

Section: Oxidations and Reductionsmentioning

confidence: 99%

HFIP in Organic Synthesis

et al. 2022

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1,1,1,3,3,3-Hexafluoroisopropanol (HFIP) is a polar, strongly hydrogen bond-donating solvent that has found numerous uses in organic synthesis due to its ability to stabilize ionic species, transfer protons, and engage in a range of other intermolecular interactions. The use of this solvent has exponentially increased in the past decade and has become a solvent of choice in some areas, such as C–H functionalization chemistry. In this review, following a brief history of HFIP in organic synthesis and an overview of its physical properties, literature examples of organic reactions using HFIP as a solvent or an additive are presented, emphasizing the effect of solvent of each reaction.

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Section: Oxidations and Reductionsmentioning

confidence: 99%

HFIP in Organic Synthesis

et al. 2022

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“…As C 2 ‐symmetric 1,2‐bis(phosphanyl)‐1,2‐dicarba‐ closo ‐dodecaboranes(12) are interesting ligands for applications in homogeneous catalysis,,,,, we have previously reported a range of palladium and platinum complexes [24a.30,31] and have now extended this concept to chiral rhodium(I) complexes ,,…”

Section: Resultsmentioning

confidence: 99%

Chiral Rhodium(I) Complexes of 1,2‐Bis‐(chloroalkoxyphosphanyl)‐ and 1,2‐Bis‐(amidoalkoxyphosphanyl)‐1,2‐dicarba‐closo‐dodecaboranes(12)

et al. 2017

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1,2‐Bis(chloroalkoxyphosphanyl)‐1,2‐dicarba‐closo‐dodecaboranes(12) and 1,2‐bis(amido‐(‐)‐menthyloxyphosphanyl)‐1,2‐dicarba‐closo‐dodecaboranes(12) were synthesised by the reaction of dilithiated 1,2‐dicarba‐closo‐dodecaborane(12) with the corresponding dichloro‐ or chloroamidophosphite. For 1,2‐bis‐(chloro‐1‐adamantyloxyphosphanyl)‐1,2‐dicarba‐closo‐dodecaborane(12) epimerisation in solution was observed and the free activation enthalpy was determined experimentally and theoretically. An indirect determination of the meso configuration was obtained by formation of the corresponding molybdenum tetracarbonyl complex. Chlorido‐bridged dimeric chiral rhodium(I) complexes showing planar or folded Rh2Cl2 rings were prepared. Density functional calculations indicate that steric and packing factors play a much more significant role than electronic effects in influencing the bending of the rhodium complexes.

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“…Consequently, the development of more efficient ligands for a range of catalytic processes is still a vital research topic. During the past decade, new families of chiral phosphines, including monodentate phosphines, − bis(aminophosphine)-type ligands, − phosphino-phosphite (P-OP), − phosphino-phosphoramidite, − spiroketal , or supramolecular-type − biphosphines, and others, , have found widespread use in the rhodium-catalyzed AH of N -acyl enamines . Among these, the past decade has witnessed the development of P -stereogenic electron-rich alkyl phosphines as highly proficient ligands. ,,− Figure shows the most relevant P -stereogenic ligands used in the rhodium-catalyzed AH of benchmark enamides (Table ).…”

Section: Asymmetric Hydrogenation Of Enamidesmentioning

confidence: 99%

Recent Advances in the Enantioselective Synthesis of Chiral Amines via Transition Metal-Catalyzed Asymmetric Hydrogenation

2021

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Chiral amines are key structural motifs present in a wide variety of natural products, drugs, and other biologically active compounds. During the past decade, significant advances have been made with respect to the enantioselective synthesis of chiral amines, many of them based on catalytic asymmetric hydrogenation (AH). The present review covers the use of AH in the synthesis of chiral amines bearing a stereogenic center either in the α, β, or γ position with respect to the nitrogen atom, reported from 2010 to 2020. Therefore, we provide an overview of the recent advances in the AH of imines, enamides, enamines, allyl amines, and N-heteroaromatic compounds.

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The use of a new carboranylamidophosphite ligand in the asymmetric Rh-catalyzed hydrogenation of α- and β-dehydroamino acid derivatives

Cited by 17 publications

References 36 publications

HFIP in Organic Synthesis

HFIP in Organic Synthesis

Chiral Rhodium(I) Complexes of 1,2‐Bis‐(chloroalkoxyphosphanyl)‐ and 1,2‐Bis‐(amidoalkoxyphosphanyl)‐1,2‐dicarba‐closo‐dodecaboranes(12)

Recent Advances in the Enantioselective Synthesis of Chiral Amines via Transition Metal-Catalyzed Asymmetric Hydrogenation

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