November 2022 | Page 4 of 5 | Chiral phosphine ligands

Li, Hui’s team published research in Angewandte Chemie, International Edition in 55 | CAS: 929294-27-9

Angewandte Chemie, International Edition 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.

Li, Hui published the artcileEnantioselective Formal Syntheses of 11 Nuphar Alkaloids and Discovery of Potent Apoptotic Monomeric Analogues, Synthetic Route of 929294-27-9, the publication is Angewandte Chemie, International Edition (2016), 55(10), 3509-3513, database is CAplus and MEDLINE.

Concise, scalable, and enantioselective formal syntheses of eight dimeric and three monomeric nuphar alkaloids were achieved, along with the construction of a stereochem. diverse collection of the first known monomeric analogs having apoptotic activity. The syntheses involved the development of highly enantioselective Bronsted acid catalyzed vinylogous Mukaiyama-Mannich reactions, which feature the unprecedented use of a supersilyl group to control the regio-, enantio- and diastereoselectivity. Biol. studies reveal that several of these novel nuphar analogs are even more potent than their dimeric natural product counterparts.

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

Yamanaka, Takuto’s team published research in Journal of the American Chemical Society in 137 | CAS: 929294-27-9

Journal of the American Chemical Society 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 C4H8Cl2S2, Computed Properties of 929294-27-9.

Yamanaka, Takuto published the artcileKinetic Resolution of Racemic Amino Alcohols through Intermolecular Acetalization Catalyzed by a Chiral Bronsted Acid, Computed Properties of 929294-27-9, the publication is Journal of the American Chemical Society (2015), 137(3), 1048-1051, database is CAplus and MEDLINE.

In the presence of nonracemic bis(triisopropylphenyl) binaphthylphosphoric or octahydrobinaphthylphosphoric acids, racemic (phenoxycarbonyl)amino alcs. such as RCH(OH)CH₂NHCO₂Ph [R = Ph, 2-naphthyl, 1,3-benzodioxol-5-yl, 2-thienyl, (E)-PhCH:CMe, i-Pr, cyclohexyl, t-Bu, TBSOCMe₂, 2-hexyl-1,3-dithiane-2-yl] underwent enantioselective acetalization and kinetic resolution with 2,3-dihydrofuran to yield nonracemic amino alcs. (R)-RCH(OH)CH₂NHCO₂Ph [R = Ph, 2-naphthyl, 1,3-benzodioxol-5-yl, 2-thienyl, (E)-PhCH:CMe, i-Pr, cyclohexyl, t-Bu, TBSOCMe₂, 2-hexyl-1,3-dithiane-2-yl; TBS = tert-butyldimethylsilyl] and (S)-O-2-tetrahydrofuranylated amino alcs.; the alcs. were isolated in 32-50% recoveries and in 94-99% ee.

Furuno, Hiroshi’s team published research in Tetrahedron Letters in 44 | CAS: 297752-25-1

Tetrahedron Letters 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 C20H21O4P, HPLC of Formula: 297752-25-1.

Furuno, Hiroshi published the artcileHighly enantioselective homogeneous catalysis of chiral rare earth phosphates in the hetero-Diels-Alder reaction, HPLC of Formula: 297752-25-1, the publication is Tetrahedron Letters (2003), 44(32), 6129-6132, database is CAplus.

Three types of rare earth (RE) complexes [Re((R)-BNP)₃] of (R)-1,1′-binaphthyl-2,2′-diylphosphates ((R)-BNP, 1; (R)-6,6′-xylyl-BNP, 2; (R)-H₈-BNP, 3) were synthesized and used as chiral Lewis acid catalysts for the hetero-Diels-Alder reaction of carbonyl compounds with the Danishefsky’s diene under homogeneous conditions. The Y[(R)-H₈-BNP]₃ (3-Y)-catalyzed reaction of aromatic aldehydes and the Yb[(R)-BNP]₃ (1-Yb)-catalyzed reaction of phenylglyoxylates afforded the corresponding cycloadducts with excellent optical purities (up to 99% ee) in high yields at room temperature The successful recycling uses of the scandium catalyst (3-Sc) are also described.

Xie, Weiqing’s team published research in Angewandte Chemie, International Edition in 52 | CAS: 929294-27-9

Xie, Weiqing published the artcileHighly Enantioselective Bromocyclization of Tryptamines and Its Application in the Synthesis of (-)-Chimonanthine, 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 Angewandte Chemie, International Edition (2013), 52(49), 12924-12927, database is CAplus and MEDLINE.

The authors report the first highly enantioselective bromocyclization of tryptamines and its application to the enantioselective synthesis of (-)-chimonanthine (I). For example, tryptamine II reacted with bromine salt III in the presence of phosphoric acid ligand IV and NaHCO₃ to give pyrrolo[2,3-b]indoledicarboxylate V in quant. yield and 96% ee.

Yuan, Jinping’s team published research in Journal of Organic Chemistry in 85 | 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 C7H13NO2, Synthetic Route of 929294-27-9.

Yuan, Jinping published the artcileBi(cyclopentyl)diol-Derived Boronates in Highly Enantioselective Chiral Phosphoric Acid-Catalyzed Allylation, Propargylation, and Crotylation of Aldehydes, Synthetic Route of 929294-27-9, the publication is Journal of Organic Chemistry (2020), 85(20), 12988-13003, database is CAplus and MEDLINE.

In this study, we disclose the catalytic addition of bi(cyclopentyl)diol-derived boronates to aldehydes promoted by chiral phosphoric acids such as (R)-TRIP-PA, allowing for the formation of enantioenriched homoallylic, propargylic, and crotylic alcs. (up to >99% enantiomeric excess (ee), diastereomeric ratio (dr) >20:1). These boronate substrates provided superior enantioselectivities, allowing for the reactions to proceed with low catalyst loading (0.5-5 mol %) and reduced reaction time (15 min at room temperature for aldehyde allylboration). A wide substrate scope was exhibited, and the novel boronates provided high enantiocontrol. Reactions with substituted allylboronates and aldehydes yielded vicinal stereogenic alcs. bearing β-tertiary or quaternary carbon centers. High enantio- and diastereoselectivities were found due to the closed six-membered chair-like transition state, with backbone modifications of the boronate and its interactions with the chiral phosphoric acid being the most likely contributing factor.

Xia, Zilei’s team published research in Organic Letters in 18 | 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 C6H8O6, SDS of cas: 929294-27-9.

Xia, Zilei published the artcileEnantioselective Bromo-oxycyclization of Silanol, SDS of cas: 929294-27-9, the publication is Organic Letters (2016), 18(1), 80-83, database is CAplus and MEDLINE.

Relying on the nucleophilicity of silanol for building up silicon-incorporated scaffold with an enantiopure tetrasubstituted carbon center remains elusive. In this report, asym. bromo-oxycyclization of olefinic silanol by using chiral anionic phase-transfer catalyst is described. This protocol provided a facile entry to a wide arrangement of enantiopure benzoxasilole in moderate to excellent enantioselectivities depending on the unique reactivity of bromine/N-benzyl-DABCO complex.

He, Shanshan’s team published research in Chirality in 30 | CAS: 297752-25-1

Chirality 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 C20H21O4P, SDS of cas: 297752-25-1.

He, Shanshan published the artcileNovel chiral ionic liquids stationary phases for the enantiomer separation of chiral acid by high-performance liquid chromatography, SDS of cas: 297752-25-1, the publication is Chirality (2018), 30(5), 670-679, database is CAplus and MEDLINE.

Novel chiral ionic liquid stationary phases based on chiral imidazolium were prepared The ionic liquid chiral selector was synthesized by ring opening of cyclohexene oxide with imidazole or 5,6-dimethylbenzimidazole, and then chem. modified by different substitute groups. Chiral stationary phases were prepared by bonding to the surface of silica sphere through thioene “click” reaction. Their enantioselective separations of chiral acids were evaluated by high-performance liquid chromatog. The retention of acid sample was related to the counterion concentration and showed a typical ion exchange process. The chiral separation abilities of chiral stationary phases were greatly influenced by the substituent group on the chiral selector as well as the mobile phase, which indicated that, besides ion exchange, other interactions such as steric hindrance, π-π interaction, and hydrogen bonding are important for the enantioselectivity. In this report, the influence of bulk solvent components, the effects of varying concentration, and the type of the counterion as well as the proportion of acid and basic additives were investigated in detail.

Furuno, Hiroshi’s team published research in Tetrahedron in 59 | CAS: 297752-25-1

Tetrahedron 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 C20H21O4P, HPLC of Formula: 297752-25-1.

Furuno, Hiroshi published the artcileChiral rare earth organophosphates as homogeneous Lewis acid catalysts for the highly enantioselective hetero-Diels-Alder reactions, HPLC of Formula: 297752-25-1, the publication is Tetrahedron (2003), 59(52), 10509-10523, database is CAplus.

Various trivalent rare earth chiral phosphate complexes [ML₃] (L = I or II, R = H, 2,6-xylyl; M = Sc, La, Ce, Nd, Gd, Ho, Y) were prepared and evaluated as a Lewis acid catalyst for the asym. hetero-Diels-Alder reaction of aldehydes with the Danishefsky’s diene. Some of them effectively promoted the reaction at room temperature in the presence or absence of achiral additives under homogeneous conditions to afford the corresponding cycloadducts with high ee’s (up to 99% ee). During these reactions, remarkably high asym. amplifications (pos. nonlinear effects) were observed as the first example in the metal ion-chiral ligand 1:3 catalytic system. A scandium catalyst bearing the H₈-BNP ligand, [ScL₃] (L = II), could be recovered after the reaction and successfully reused for the next round of reactions. In addition, the hetero-Diels-Alder reaction of α-keto esters was effectively catalyzed by [YL₃] (L = I, R = H) without any additives thus producing the asym. quaternary carbon in excellent enantioselectivities (up to >99% ee).

Romanov-Michailidis, Fedor’s team published research in Organic Letters in 15 | CAS: 929294-27-9

Romanov-Michailidis, Fedor published the artcileEnantioselective Organocatalytic Iodination-Initiated Wagner-Meerwein Rearrangement, COA of Formula: C50H65O4P, the publication is Organic Letters (2013), 15(22), 5890-5893, database is CAplus and MEDLINE.

The present manuscript describes a high-yielding enantioselective semipinacol transposition, initiated by an electrophilic iodination event. The title transformation makes use of the anionic phase-transfer catalysis (PTC) paradigm for chirality induction. Thus, when combined appropriately, the insoluble cationic iodinating reagent and the lipophilic phosphoric acid act as an efficient source of chiral iodine that performs the semipinacol transposition of strained allylic alcs. to β-iodo spiroketones in good yields and with high levels of diastereo- and enantio-induction. The product β-iodo spiroketones could be derivatized stereospecifically and without stereoerosion, giving rise to products inaccessible directly from a semipinacol rearrangement.

Romanov-Michailidis, Fedor’s team published research in Angewandte Chemie, International Edition in 52 | CAS: 929294-27-9

Romanov-Michailidis, Fedor published the artcileEnantioselective Organocatalytic Fluorination-Induced Wagner-Meerwein Rearrangement, Formula: C50H65O4P, the publication is Angewandte Chemie, International Edition (2013), 52(35), 9266-9270, database is CAplus and MEDLINE.

The synthesis of the target compounds was achieved (optimized conditions) using 1-(chloromethyl)-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane tetrafluoroborate(1-) (Selectfluor) as fluorination agent and a chiral dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepin 4-oxide as catalyst. The title compounds thus formed included 3′,4′-dihydro-2′-(fluoro)spiro[cyclopentane-1,1′(2′H)-naphthalen]-2-one derivatives, 3′,4′-dihydro-2′-(fluoro)spiro[cyclobutane-1,1′(2′H)-naphthalen]-2-one derivatives and 3′,4′-dihydro-2′-(fluoro)spiro[cyclohexane-1,1′(2′H)-naphthalen]-2-one derivatives The title compounds thus formed included a chiral spiro[cyclobutane-naphthalenone] derivative (I). Reactants included 1-(3,4-dihydro-1-naphthalenyl)cyclobutanol, 1-(2H-1-benzopyran-4-yl)cyclobutanol, 1-(3,4-dihydro-1-naphthalenyl)cyclopentanol 1-(3,4-dihydro-1-naphthalenyl)cyclopropanol etc.