含金刚烷基团的新型手性单齿亚磷酸酯配体的合成及其在不对称1,4-共轭加成反应中的应用

以轴手性的BINOL/H8-BINOL(BINOL为联苯酚)和大位阻的金刚烷酰氯为原料,合成了系列新型手性单齿亚磷酸酯配体,并应用于Cu催化的二乙基锌对环烯酮的不对称1,4.共轭加成反应中.结果表明,配体结构中部分氢化的2,2'-(1,1'-联萘基)亚磷酸酯单元和金刚烷基团,有助于改善反应的对映选择性,对映选择性最高可...     

Dendritic BINOL ligands for asymmetric catalysis: effect of the linking positions and generations of the dendritic wedges on catalyst properties

Three types of new chiral BINOL ligands (2, 3 and 4) bearing dendritic wedges have been synthesized through coupling reaction between 3-hydroxymethyl-2,2′-bis(methoxymethyl)-1,1′-binaphthol (7), 6,6′-dihydroxymethyl-2,2′-bis(methoxymethyl)-1,1′-binaphthol (12), 6-hydroxymethyl-2,2′-bis(methoxymethyl)-1,1′-binaphthol (15) and Fréchet-type polyether dendritic benzyl bromide, followed by deprotection of methoxymethyl groups by ⁱPrOH/HCl, respectively. These new ligands obtained were assessed in enantioselective Lewis acid-catalyzed addition of diethylzinc to benzaldehyde. Compared to the enantioselectivity observed with dendrimer 1 bearing the dendritic wedges at 3,3′-positions of the binaphthyl backbone, higher enantioselectivity for all these ligands was observed. Difference in the effect of linking positions and generations on enantioselectivity and/or activity for all three kinds of dendritic ligand-derived catalysts was observed. Among these dendritic ligands, (R)-3/Ti(IV) catalyst with the dendritic wedges at 6,6′-positions of BINOL gave the highest enantioselectivity (up to 87% ee).     

Immobilization of BINOL by cross-linking copolymerization of styryl derivatives with styrene, and applications in enantioselective Ti and Al Lewis acid mediated additions of Et2Zn and Me3SiCN to aldehydes and of diphenyl nitrone to enol ethers

The chiral ligand 1,1'-bi-2-naphthol (BINOL) has been succesfully immobilized on polystyrene. Several dendritic and non-dendritic BINOL derivatives (3, and 13-17), bearing at least two polymerizable styryl groups, were prepared and fully characterized. Suspension copolymerization of the MOM- or TIPS-protected cross-linking BINOL ligands (MOM = methyloxymethyl, TIPS = triisopropylsilyl) with styrene, cleavage of the protecting-groups, and loading with a Lewis-acid afforded catalytically active polystyrene-supported BINOLates. The polymer-bound BINOLs p-3, and p-13-p-16 were tested in the Ti-BINOLate-mediated addition of Et2Zn to PhCHO. The enantioselectivities (up to 93%) and conversions obtained with the polymer-bound catalysts were in most cases identical (within experimental error) to those obtained with the unsubstituted 1,1'-bi-2-naphthol and with the non-polymerized BINOL cross-linkers under homogeneous conditions. Special focus was put on the reusability of the supported catalyst: the polymer-beads were used in up to 20 consecutive catalytic runs, with the best polymers showing no or only minor loss of selectivity. BINOL-polymers p-17, obtained by copolymerization of a 3,3'-distyryl-substituted BINOL 17a with styrene, were used in the BINOL. AlMe-mediated cycloaddition of diphenyl nitrone with alkyl vinyl ethers. In all cases the exo/endo selectivity (> or =92:8) and the enantioselectivities with which the exo-cycloadducts were formed (> or =95%) correspond to those observed in the homogeneous reactions. A dendritically cross-linked BINOL-polymer was also employed in the Ti-BINOLate-mediated cyanosilylation of pivalaldehyde. The enantiopurity of the cyanohydrine obtained in the first run was as high as in the homogeneous reaction (72%); surprisingly the catalytic performance of the supported catalyst increased steadily during the first catalytic cycles to reach 83%. Thus, cross-linking BINOLs can be succesfully incorporated into a polystyrene matrix (without racemization!) to give polymer-bound BINOL ligands that give excellent performance over many catalytic cycles with catalytic activities comparable with those of soluble analogues.     

Asymmetric Meerwein-Ponndorf-Verley reduction catalyzed by a new type of chiral binaphthol-samarium complex

A new type of chiral 1,1'-binaphthol(BINOL) derived samarium complex, preparedfrom (R)- or (S)-BINOL and SmCl3, serves as an enantioselective catalyst for the Meerwein-Ponndorf-Verley (MPV) reduction in the presence of Molecular Sieves 4A(MS 4A). Moderate enantioselectivity was obtained. Kinetic studies show slight decrease of the enantiomeric excess with the conversion.     

Asymmetric alkyne addition to aldehydes catalyzed by Schiff bases made from 1,1′-bi-2-naphthol and chiral benzylic amines

Several 1,1′-bi-2-naphthol (BINOL)-based Schiff bases were prepared from the condensation of (R)-3,3′-diformyl BINOL with chiral benzylic amine derivatives. These compounds were used to catalyze the reaction of phenylacetylene with aldehydes in the presence of ZnEt₂ with up to 85% ee and 83% yield.     

手性联二萘酚衍生物催化的苯乙炔与苯甲醛不对称加成反应

以手性联二萘酚为原料,合成了3,3′位取代的手性联二萘酚衍生物,研究了该衍生物配体在二乙基锌存在下,催化苯乙炔与苯甲醛的不对称加成反应,产物的产率为73%,e.e.值为40%。 研究结果表明,手性联二萘酚衍生物结构的微小变化导致催化产物构型的改变。     

聚合物负载的手性联二萘酚的合成及其在不对称催化中的应用进展

作为一种有机配体, 手性1,1'-联二萘酚(BINOL)被广泛应用于过渡金属催化的均相不对称有机反应. 为克服均相催化剂不易回收重复使用等缺陷, 人们深入研究了聚合物负载手性BINOL催化剂的方法. 总结了近年来聚合物负载手性BINOL催化剂的合成及其在不对称有机催化中的应用, 并对负载型BINOL催化剂进行了展望.     

Facile synthesis of 6-iodo-2,2′-dipivaloyloxy-1,1′-binaphthyl, a key intermediate of high reactivity for selective palladium-catalyzed monofunctionalization of the 1,1′-binaphthalene core

A high-yielding procedure for selective monoiodination of 2,2′-dihydroxy-1,1′-binaphthyl (BINOL) is reported. 6-Iodo-2,2′-dipivaloyloxy-1,1′-binaphthyl, obtained in three steps starting from BINOL in 88% overall yield, proved to be a highly efficient substrate in various palladium-catalyzed coupling (Stille, Heck, Sonogashira, and Suzuki coupling) and carbonylation reactions compared to the analogous 6-bromo derivative.     

(��)-1,1��-Binaphthalene-2,2��-diol-derived phosphoric diester: immobilization on polyethylene glycol support and application in the Pudovik reaction

(±)-1,1??-Binaphthalene-2,2??-diol (BINOL) was immobilized on polyethylene glycol (PEG) by means of triazole linkers, which were constructed by the [3+2] cycloaddition between azide and ethynyl fragments, preliminary incorporated into the molecules of these reactants. Treatment of these BINOL derivatives with phosphorus oxychloride leads to the corresponding PEG-immobilized 1,1??-binaphthalene-2,2??-diylphosphoric acids. The latter efficiently catalyze the Pudovik reaction and can be reused without loss of catalytic activity.     

Embedding an allylmetal dimer in a chiral cavity: the unprecedented stereoselectivity of a twofold wittig [1,2]-rearrangement

After alpha,alpha'-dimetalation, both 2,2'-diallyloxy-1,1'-binaphthyl and 2,2'-di-2-methylallyloxy-1,1'-binaphthyl undergo the Wittig rearrangement with perfect diastereoselectivity. When racemic 1,1'-binaphthyl-2,2'-diol ("BINOL") is used as the starting material, it gives rise to a 1:1 mixture of antipodal stereoisomers, whereas enantiomerically pure (M)-2,2'-diallyloxy-1,1'-binaphthyl affords (M)-(S,S)-1,1-(1,1'-binaphthyl-2,2'-diyl)bis(2-propen-1-ol) as the sole product. The (M)-(S,S)/(P)-(R,R) mixture resulting from the rearrangement of racemic 2,2'-diallyloxy-1,1'-binaphthyl can be effectively subjected to a kinetic racemate resolution by applying the Sharpless-Katsuki asymmetric epoxidation. The single-sided Wittig rearrangement of 2-allyloxy-2'-propyloxy-1,1'-binaphthyl proceeds without any diastereoselectivity as this substrate can only be monometalated and hence is incapable of intramolecular aggregate formation which is instrumental for the observed stereoselectivity.     

Asymmetric [2 + 1] Cycloaddition Reactions of 1-Seleno-2-silylethene

The reaction of (E)-1-(phenylseleno)-2-(trimethylsilyl)ethene (1) and vinyl ketones 2a-d in the presence of a chiral Lewis acid prepared from TiCl(4), Ti(O(i)Pr)(4), (R)- or (S)-1,1'-binaphthol (BINOL), and MS4A gave enantiomerically enriched cis cyclopropane products 3a-d. The enantiomeric excess and chemical yield varied depending on the ratio of TiCl(4) and Ti(O(i)Pr)(4) to 1. Reproducible results (43-47% ee/33-41% yields) for cis-1-acetyl-2-[(phenylseleno)(trimethylsilyl)methyl]cyclopropane (3a) were obtained using 1.1 equiv of TiCl(4), 0.54-0.65 equiv of Ti(O(i)Pr)(4), and 1.65 equiv of BINOL. The observed enantioselectivity was explained by consideration of the structure of the postulated intermediates, alkoxy titanium-carbonyl complexes, via ab initio MO calculations.     

Cu<Superscript>I</Superscript>-catalyzed <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>’-diarylation of diamines of adamantane series

A copper(I) complex-catalyzed N,N’-diarylation of diamines based on 1,3-disubstituted adamantane, using aryl iodides bearing electron-donating and electron-withdrawing substituents, was studied. In the case of 2,2’-(adamantane-1,3-diyl)ethanediamine, the optimal catalyst system is CuI—2-(isobutyryl)cyclohexanone—Cs₂CO₃—DMF. The highest yield of diarylation product was reached in the case of 4-methoxyiodobenzene (79%). In the case of more spatially hindered adamantane-1,3-diyldimethanamine, 1,1’-binaphthalene-2,2’-diol (BINOL) should be used, with the highest yield of the target product (84%) being reached in the reaction with iodobenzene.     

Lewis acid-activated chiral leaving group: enantioselective electrophilic addition to prochiral olefins

A new strategy using a BINOL derivative as a chiral leaving group and Lewis acid has been developed for enantioselective alkylation of prochiral olefins. (R)-2,2'-Bis[2-(trimethylsilyl)ethoxymethyl]-1,1'-binaphthol is demonstrated to be an effective reagent for enantioselective hydroxymethylation of silyl enol ethers and trisubstituted alkenes. Electrophilic addition to prochiral olefins is accompanied by cleavage of an acetal that is dual activated by SnCl4 and the delta-effect of silicon through the S(N)2 substitution process. Enantioselective synthesis of cyclic terpenes is also described using this strategy.     

A novel trinuclear titanium(IV) complex with a C3 axis along Ti1–Ti2–Ti3 containing 3-[(1H-1,2,4-triazol-1-yl)methyl]-BINOLate ligands: synthesis,structure, and reactivity

A new modified BINOL, (S)-3-[(1H-1,2,4-triazol-1-yl)methyl]-1,1′-binaphthol, was prepared. In the presence of titanium tetraisopropoxide, this ligand showed moderate catalytic properties for the asymmetric addition of diethylzinc to aldehydes. By treating rac-3-[(1H-1,2,4-triazol-1-yl)methyl]-1,1′-binaphthol with excess titanium tetraisopropoxide, a novel trinuclear titanium(IV) complex was obtained. A C₃ axis along Ti1–Ti2–Ti3 is present in the molecule.     

A planar silacyclobutane, 1,1-(rac-1,1′-bi-2-naphthoxy)-1-silacyclobutane and its unusual reaction with bis(1,5-cyclooctadiene)platinum(0)

The synthesis, characterization and X-ray crystal structure of 1,1-(rac-1,1′-bi-2-naphthoxy)-1-silacyclobutane (1) are reported and reveal an unusual planar conformation with a Si-βC distance of 2.302 (5) Å. Reaction of 1 with either stoichiometric or catalytic amounts of bis(1,5-cyclooctadiene)platinum(0) {Pt(cod)₂} gave 1,1′-bi-2-naphthol (BINOL), rather than the expected insertion products or polymer. A mechanism is proposed based on insertion of the Pt(cod) into 1 followed by hydride transfers via the Pt center to the 1,1′-bi-2-naphthoxy group. Anionic ring-opening polymerization of 1 is also reported and gave the poly(carbosilane) (4).     

An Enantioselective Bidentate Auxiliary Directed Palladium‐Catalyzed Benzylic C−H Arylation of Amines Using a BINOL Phosphate Ligand

A new enantioselective palladium(II)‐catalyzed benzylic C?H arylation reaction of amines is enabled by the bidentate picolinamide (PA) directing group. This reaction provides the first example of enantioselective benzylic γ‐C?H arylations of alkyl amines, and proceeds with up to 97 % ee. The 2,2′‐dihydroxy‐1,1′‐binaphthyl (BINOL) phosphoric acid ligand, Cs₂CO₃, and solvent‐free conditions are essential for high enantioselectivity. Mechanistic studies suggest that multiple BINOL ligands are involved in the stereodetermining C?H palladation step.     

树脂固定化手性联萘酚-钛催化剂的合成及其催化特性研究

自从Ｍｅｒｒｉｆｉｅｌｅｄ首创多肽的固相合成以来 ,以聚苯乙烯树脂为支持物的合成方法在化学及生物化学等领域得到广范应用[1～ 3] .作为该方法的一个新的发展方向 ,将手性配体联接在多聚物上用于非均相不对称催化已成为当前不对称合成的热门领域之一 .近年来踊现出大量多聚物固定化的手性不对称催化剂 ,在二乙基锌对醛的不对称加成[4] 及Ｄｉｅｌｓ Ａｌｄｅｒ等[5] 反应中显示出优良的不对称催化能力 .光学活性的 1 ,1’ 联萘 2 酚 (ＢＩＮＯＬ)是不对称催化中应用最广泛的配体之一[6～ 9] .为了将ＢＩＮＯＬ引入非均相不对称催化 ,我…     

Development of Ar‐BINMOL‐Derived Atropisomeric Ligands with Matched Axial and sp3 Central Chirality for Catalytic Asymmetric Transformations

Recently, academic chemists have renewed their interest in the development of 1,1′‐binaphthalene‐2,2′‐diol (BINOL)‐derived chiral ligands. Six years ago, a working hypothesis, that the chirality matching of hybrid chirality on a ligand could probably lead to high levels of stereoselective induction, prompted us to use the axial chirality of BINOL derivatives to generate new stereogenic centers within the same molecule with high stereoselectivity, obtaining as a result sterically favorable ligands for applications in asymmetric catalysis. This Personal Account describes our laboratory's efforts toward the development of a novel class of BINOL‐derived atropisomers bearing both axial and sp³ central chirality, the so‐called Ar‐BINMOLs, for asymmetric synthesis. Furthermore, on the basis of the successful application of Ar‐BINMOLs and their derivatives in asymmetric catalysis, the search for highly efficient and enantioselective processes also compelled us to give special attention to the BINOL‐derived multifunctional ligands with multiple stereogenic centers for use in catalytic asymmetric reactions.

     

联萘酚与固体支撑双层类脂膜相互作用

采用循环伏安法、交流阻抗法研究了联萘酚(BINOL)与固体支撑双层类脂膜(s-BLM)之间的相互作用.结果表明,联萘酚通过氢键、疏水作用与s-BLM发生相互作用.随着相互作用时间的延长,联萘酚/s-BLM体系中的氧化峰电流先增大后减小,表明联萘酚逐渐破坏s-BLM的整体性,诱导膜内部形成微孔通道.联萘酚的浓度越大,联萘酚分子通过s-BLM的渗透时间越短.此外,随着卵磷脂浓度和胆固醇含量的增加,s-BLM的膜电阻变大,联萘酚渗透通过s-BLM速率减小,导致其对s-BLM的渗透性能减弱.     

Syntheses and Crystal Structures of Chiral BINOL Derivatives and Their Applications in Enantioselective Lewis Acid Catalyzed Addition of Diethylzinc to Aldehydes

Two novel chiral BINOL derivatives with bis(benzylamine) groups at the 3,3- positions have been synthesized through the condensation reaction between 2,2'-bis(methoxy- methyleneoxy)-1,1'-binaphthyl-3,3'-dicarboxylic acid and benzylamine or N-phenyl benzylamine in the presence of triethylamine. Suitable single crystal of (R)-N,N'-dibenzyl-2,2'-dihydroxy-1, 1'-binaphthly-3,3'-diformamide (R)-3 for X-ray diffraction was obtained by recrystallization at room temperature from the mixture solvents. Crystallographic data of (R)-3: C40H36N2O6, Mr = 640.71, monoclinic, space group P21, a = 6.746(3), b = 21.883(9), c = 11.723(5) , β = 104.605(7)°, Z = 2, V = 1674.7(12) 3, Dc = 1.271 g/cm3, F(000) = 676, R = 0.0729, wR = 0.1687 and μ(MoKα) = 0.086 mm-1. Two chiral BINOL ligands were found to be effective in the enantioselective addition of diethylzinc to aldehydes and much different enantioselectivity was observed both in the presence and absence of Ti(OiPr)4. In the former case, (R)-3 showed moderate enantioselectivity, which was lower than that of (R)-BINOL's; and in the latter case, (R)-4 gave the highest enan- tioselectivity up to 93.3% ee.*