November 2022 | Page 2 of 5 | Chiral phosphine ligands

Zhang, Hua’s team published research in ACS Catalysis in 12 | CAS: 929294-27-9

ACS Catalysis published new progress about 929294-27-9. 929294-27-9 belongs to chiral-phosphine-ligands, auxiliary class Chiral Phosphoric Acids, name is R-3,3′-Bis(2,4,6-triisopropylphenyl)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2,2′-diyl hydrogenphosphate, and the molecular formula is C20H21ClN4O4, Category: chiral-phosphine-ligands.

Zhang, Hua published the artcileVisible-Light-Mediated Formal Carbene Insertion Reaction: Enantioselective Synthesis of 1,4-Dicarbonyl Compounds Containing All-Carbon Quaternary Stereocenter, Category: chiral-phosphine-ligands, the publication is ACS Catalysis (2022), 12(9), 5510-5516, database is CAplus.

Authors developed an efficient visible-light-mediated formal carbene insertion reaction of 1,3-diketones with diazoesters for the construction of enantioenriched 1,4-dicarbonyl compounds with a quaternary carbon center. Combining visible light and a Bronsted acid catalyst, chiral 1,4-dicarbonyl compounds were achieved in good yields with high enantioselectivities by a photochem. carbene transfer protocol.

Referemce:
https://en.wikipedia.org/wiki/Phosphine_ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

Wu, Zijun’s team published research in ACS Catalysis in 7 | CAS: 297752-25-1

ACS Catalysis published new progress about 297752-25-1. 297752-25-1 belongs to chiral-phosphine-ligands, auxiliary class Chiral Phosphoric Acids, name is (R)-4-Hydroxy-8,9,10,11,12,13,14,15-octahydrodinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide, and the molecular formula is C5H10Cl3O3P, Safety of (R)-4-Hydroxy-8,9,10,11,12,13,14,15-octahydrodinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide.

Wu, Zijun published the artcileEnantioselective Medium-Ring Lactone Synthesis through an NHC-Catalyzed Intramolecular Desymmetrization of Prochiral 1,3-Diols, Safety of (R)-4-Hydroxy-8,9,10,11,12,13,14,15-octahydrodinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide, the publication is ACS Catalysis (2017), 7(11), 7647-7652, database is CAplus.

A highly enantioselective intramol. annulation reaction of 1,3-diols catalyzed by a triazolium N-heterocyclic carbene (NHC) precatalyst is disclosed, affording the corresponding medium-sized lactones in moderate to good yields with high enantioselectivities. It is worth noting that this compatible catalytic system was successfully applied to assemble a broad range of chiral medium-sized lactones, including ones with eight-, nine-, ten-, eleven-, and twelve-membered rings.

Wu, Haibo’s team published research in Journal of Separation Science in 37 | CAS: 297752-25-1

Journal of Separation Science published new progress about 297752-25-1. 297752-25-1 belongs to chiral-phosphine-ligands, auxiliary class Chiral Phosphoric Acids, name is (R)-4-Hydroxy-8,9,10,11,12,13,14,15-octahydrodinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide, and the molecular formula is C15H24O2, Computed Properties of 297752-25-1.

Wu, Haibo published the artcileNovel chiral stationary phases based on peptoid combining a quinine/quinidine moiety through a C9-position carbamate group, Computed Properties of 297752-25-1, the publication is Journal of Separation Science (2014), 37(8), 934-943, database is CAplus and MEDLINE.

By connecting a quinine or quinidine moiety to the peptoid chain through the C9-position carbamate group, the authors synthesized two new chiral selectors. After immobilizing them onto 3-mercaptopropyl-modified silica gel, two novel chiral stationary phases were prepared With neutral, acid, and basic chiral compounds as analytes, the authors evaluated these two stationary phases and compared their chromatog. performance with chiral columns based on quinine tert-Bu carbamate and the previous peptoid. From the resolution of neutral and basic analytes under normal-phase mode, the new stationary phases exhibited much better enantioselectivity than the quinine tert-Bu carbamate column; the peptoid moiety played an important role in enantiorecognition, which controlled the elution orders of enantiomers; the assisting role of the cinchona alkaloid moieties was observed in some separations Under acid polar organic phase mode, cinchona alkaloid moieties introduced excellent enantiorecognitions for chiral acid compounds; in some separations, the peptoid moiety affected enantioseparations as well. Overall, chiral moieties with specific enantioselectivity improve the performance of peptoid chiral stationary phase efficiently.

Liang, Kangjiang’s team published research in Journal of Organic Chemistry in 83 | CAS: 929294-27-9

Journal of Organic Chemistry published new progress about 929294-27-9. 929294-27-9 belongs to chiral-phosphine-ligands, auxiliary class Chiral Phosphoric Acids, name is R-3,3′-Bis(2,4,6-triisopropylphenyl)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2,2′-diyl hydrogenphosphate, and the molecular formula is C50H65O4P, Category: chiral-phosphine-ligands.

Liang, Kangjiang published the artcileEnantioselective Radical Cyclization of Tryptamines by Visible Light-Excited Nitroxides, Category: chiral-phosphine-ligands, the publication is Journal of Organic Chemistry (2018), 83(18), 10948-10958, database is CAplus and MEDLINE.

Nitroxides can absorb both UV and visible light, and their electron can be excited from the π-bonding orbital to the antibonding π* orbital or the n-bonding orbital to the antibonding π* orbital, resp. Despite the reported UV-induced hydrogen atom transfer (HAT) process, the potential of nitroxides for visible light-excited photosynthesis is underexplored. Here we demonstrate that nitroxide can convert indole to its radical through a visible light-induced HAT process. A chiral phosphoric acid-catalyzed cyclization of the in situ-formed imine radical, followed by trapping by another mol. of nitroxide, provides the product in high yield and enantioselectivity. To highlight the novelty and efficiency of this strategy, an asym. total synthesis of natural product (-)-verrupyrroloindoline was accomplished in 5 steps.

Czako, Barbara’s team published research in Journal of Medicinal Chemistry in 64 | CAS: 2055761-19-6

Journal of Medicinal Chemistry published new progress about 2055761-19-6. 2055761-19-6 belongs to chiral-phosphine-ligands, auxiliary class Spiro[4.5], name is (3S,4S)-3-Methyl-2-oxa-8-azaspiro[4.5]decan-4-amine dihydrochloride, and the molecular formula is C9H20Cl2N2O, Application In Synthesis of 2055761-19-6.

Czako, Barbara published the artcileDiscovery of 6-[(3S,4S)-4-Amino-3-methyl-2-oxa-8-azaspiro[4.5]decan-8-yl]-3-(2,3-dichlorophenyl)-2-methyl-3,4-dihydropyrimidin-4-one (IACS-15414), a Potent and Orally Bioavailable SHP2 Inhibitor, Application In Synthesis of 2055761-19-6, the publication is Journal of Medicinal Chemistry (2021), 64(20), 15141-15169, database is CAplus and MEDLINE.

Src homol. 2 (SH2) domain-containing phosphatase 2 (SHP2) plays a role in receptor tyrosine kinase (RTK), neurofibromin-1 (NF-1), and Kirsten rat sarcoma virus (KRAS) mutant-driven cancers, as well as in RTK-mediated resistance, making the identification of small-mol. therapeutics that interfere with its function of high interest. Our quest to identify potent, orally bioavailable, and safe SHP2 inhibitors led to the discovery of a promising series of pyrazolopyrimidinones that displayed excellent potency but had a suboptimal in vivo pharmacokinetic (PK) profile. Hypothesis-driven scaffold optimization led us to a series of pyrazolopyrazines with excellent PK properties across species but a narrow human Ether-á-go-go-Related Gene (hERG) window. Subsequent optimization of properties led to the discovery of the pyrimidinone series, in which multiple members possessed excellent potency, optimal in vivo PK across species, and no off-target activities including no hERG liability up to 100μM. Importantly, compound 30 (IACS-15414) potently suppressed the mitogen-activated protein kinase (MAPK) pathway signaling and tumor growth in RTK-activated and KRAS^mut xenograft models in vivo.

Ray, Sumit K.’s team published research in Organic Letters in 21 | CAS: 929294-27-9

Organic Letters published new progress about 929294-27-9. 929294-27-9 belongs to chiral-phosphine-ligands, auxiliary class Chiral Phosphoric Acids, name is R-3,3′-Bis(2,4,6-triisopropylphenyl)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2,2′-diyl hydrogenphosphate, and the molecular formula is C50H65O4P, Recommanded Product: R-3,3′-Bis(2,4,6-triisopropylphenyl)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2,2′-diyl hydrogenphosphate.

Ray, Sumit K. published the artcileA General Catalytic Route to Enantioenriched Isoindolinones and Phthalides: Application in the Synthesis of (S)-PD 172938, Recommanded Product: R-3,3′-Bis(2,4,6-triisopropylphenyl)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2,2′-diyl hydrogenphosphate, the publication is Organic Letters (2019), 21(2), 417-422, database is CAplus and MEDLINE.

Chiral Bronsted acid catalyzed enantioselective syntheses of isoindolinones, e.g. I, and phthalides have been accomplished via tandem Mannich-lactamization and aldol-lactonization reactions, resp. A variety of enantioenriched isoindolinones (up to 99% ee) and phthalides (up to 85% ee) containing α-diazoesters were afforded in excellent yields. Furthermore, a concise synthesis of (S)-PD 172938 has been demonstrated by using this protocol.

Romanov-Michailidis, Fedor’s team published research in Chemistry – A European Journal in 21 | CAS: 929294-27-9

Chemistry – A European Journal published new progress about 929294-27-9. 929294-27-9 belongs to chiral-phosphine-ligands, auxiliary class Chiral Phosphoric Acids, name is R-3,3′-Bis(2,4,6-triisopropylphenyl)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2,2′-diyl hydrogenphosphate, and the molecular formula is C50H65O4P, Synthetic Route of 929294-27-9.

Romanov-Michailidis, Fedor published the artcileEnantioselective Halogenative Semi-Pinacol Rearrangement: Extension of Substrate Scope and Mechanistic Investigations, Synthetic Route of 929294-27-9, the publication is Chemistry – A European Journal (2015), 21(14), 5561-5583, database is CAplus and MEDLINE.

The present Full Paper article discloses a survey of our recent results obtained in the context of the enantioselective halogenation-initiated semi-pinacol rearrangement. Commencing with the fluorination/semi-pinacol reaction first and moving to the heavier halogens (bromine and iodine) second, the scope and limitations of the halogenative phase-transfer methodol. will be discussed and compared. An extension of the fluorination/semi-pinacol reaction to the ring-expansion of five-membered allylic cyclopentanols will be also described, as well as some preliminary results on substrates prone to desymmetrization will be given. Finally, the present manuscript will culminate with a detailed mechanistic investigation of the canonical fluorination/semi-pinacol reaction. Our mechanistic discussion will be based on in situ reaction progress monitoring, complemented with substituent effect, kinetic isotopic effect and non-linear behavior studies.

Gao, Zeng’s team published research in Chemical Communications (Cambridge, United Kingdom) in 56 | CAS: 929294-27-9

Chemical Communications (Cambridge, United Kingdom) published new progress about 929294-27-9. 929294-27-9 belongs to chiral-phosphine-ligands, auxiliary class Chiral Phosphoric Acids, name is R-3,3′-Bis(2,4,6-triisopropylphenyl)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2,2′-diyl hydrogenphosphate, and the molecular formula is C50H65O4P, Product Details of C50H65O4P.

Gao, Zeng published the artcileChiral Bronsted acid-catalyzed dynamic kinetic resolution of atropisomeric ortho-formyl naphthamides, Product Details of C50H65O4P, the publication is Chemical Communications (Cambridge, United Kingdom) (2020), 56(53), 7265-7268, database is CAplus and MEDLINE.

Despite the widespread use of naphthamide atropisomers in biol. active compounds and asym. catalysis, few catalytic methods have succeeded in the enantioselective synthesis of these compounds Herein, a chiral Bronsted acid (CBA) catalysis strategy was developed for readily scalable dynamic kinetic resolution of challenging ortho-formyl naphthamides with pyrrolylanilines. The chiral axis of the atropisomeric amide and a stereogenic center were simultaneously established for a new family of potential biol. active pyrrolopyrazine compounds with high enantio- and diastereoselectivities (up to >20 : 1 d.r. and 98 : 2 e.r.). Epimerization experiments of its derivatives reveal that the N-substitution of the nearby stereogenic center could affect the configurational stability of the axially chiral aromatic amides. These results might be useful for the construction of other kinds of novel axially chiral mols. with a low rotational barrier.

Romanov-Michailidis, Fedor’s team published research in Organic Letters in 16 | CAS: 929294-27-9

Romanov-Michailidis, Fedor published the artcileEnantioselective Catalytic Fluorinative Aza-semipinacol Rearrangement, Recommanded Product: R-3,3′-Bis(2,4,6-triisopropylphenyl)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2,2′-diyl hydrogenphosphate, the publication is Organic Letters (2014), 16(19), 4988-4991, database is CAplus and MEDLINE.

An efficient and highly stereoselective fluorinative aza-semipinacol rearrangement is described. The catalytic reaction requires use of Selectfluor in combination with the chiral, enantiopure phosphate anion derived from acid. Under optimized conditions, cyclopropylamines were transformed into β-fluoro cyclobutylimines in good yields and high levels of diastereo- and enantiocontrol. Furthermore, the optically active cyclobutylimines were reduced diastereoselectively with L-Selectride in the corresponding fluorinated amines, compounds of significant interest in the pharmacol. industry.

Romanov-Michailidis, Fedor’s team published research in Chemical Communications (Cambridge, United Kingdom) in 50 | CAS: 929294-27-9

Romanov-Michailidis, Fedor published the artcileEnantioselective halogenative semi-pinacol rearrangement: a stereodivergent reaction on a racemic mixture, Safety of R-3,3′-Bis(2,4,6-triisopropylphenyl)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2,2′-diyl hydrogenphosphate, the publication is Chemical Communications (Cambridge, United Kingdom) (2014), 50(88), 13461-13464, database is CAplus and MEDLINE.

An efficient, quant. deracemization strategy for optically inactive allylic cycloalkanols, e.g. I, has been achieved using the biphasic halogenative semi-pinacol reaction protocol. The resultant β-halo spiroketones, containing three contiguous stereogenic centers, e.g. II, were easily recovered with high diastereomeric and enantiomeric purities following conventional silica gel chromatog. The optically active products could be further manipulated chem., affording synthetically interesting scaffolds with complete preservation of stereoisomeric integrity.