Binaphthyl crystal structure

Crystal structure of 1, l -binaphthyl-8,8 -dicarboxylic acid Czugler, M., Weber, E. Unpublished result (1985)... 

The oxidation of phenols forming aryloxyl radicals was first recognized by Pummerer and Frankfurter in 1914," who reacted 2,2 -dihydroxy-l,l -binaphthyl with ferricyanide, and isolated dimers and trimers of the radical 20 (equation 8), which was later observed by ESR." Many further examples were studied by Goldschmidt, Muller, and others," and an X-ray crystal structure confirmed dimer formation with C—O bonding at the 4-position for 3-bromo-2,4,6-triphenylphenoxyl. ... 

While working on a related series of non-polymeric model compounds, we prepared the binaphthyl derivative 35 by the synthetic route depicted in Scheme 3.17 [34, 51] The yield was particularly poor (10%) but, nevertheless, a full characterization of 35 was achieved. The crystal structure of 35 has been elucidated from single crystals obtained from THF [51] and reveals that the molecule adopts a folded conformation in the solid state that is characterized by an almost parallel... 

A number of other crown ether hosts with more than one primary binding site have been synthesised [17,63]. CPK molecular models of the chiral bismacrocycle (5)-(42) reveal that this host possesses a jaws-like receptor site in which the binaphthyl unit can serve as a hinge. The X-ray crystal structure [64] of the 1 1 complex ((S)-(42)-H3N(CH2)4NHj2PFj) shown in Fig. 5 possesses the expected structure. The host (S)-(42) has been used [5] to bind other bifunctional guests. 

Rh4(/r-bpnap)(CO)io (bpnap = 2,2 -bis[(l,l -biphenyl-2,2 -diyl)phosphite]-l,l -binaphthyl) is a catalyst precursor for the isomerization and hydroformylation of 1-octene. The cluster was synthesized by reaction of Rh2(CO)4Cl2 with bpnap under CO. Two isomers were identified. The hydroformylation of a-methylstyrene with mononuclear Rh(acac)(CO)2 and R-(- -)-bpnap gave essentially no ee of 3-phenylbutanal. The crystal structure established that the bpnap ligand bridged two rhodium atoms of a tetrahedral metal framework. The same isomers were formed from... 

The 16- and 18-membered P2 macrocycles (131 n = 2 and R = Me or OMe n = 3, R = OMe) have been synthesized from the corresponding terminal /7-toluenesulfonate esters and dilithium 1,2-phenylenebis(methylphosphide) under high-dilution conditions <92CB679>. The compoimds (131 n = 3, R = OMe) were obtained in 87% yield. X-ray crystal structure analyses of the C and C2 diastereomers of (131 = 2, R = Me) and the C] diastereomer of (131 = 2, R = OMe) and its nickel(ll) chloride adduct were performed. In later work, the compounds (132 n = 2 ) were prepared in optically active form from (S)-l,r-binaphthyl-2,2 -diol and square-planar complexes... 

The same group also reported that when cadmium nitrate or perchlorate salts were used in the preparation of the MOF, two different MOF structures can be obtained with the same chiral binaphthyl ligand [130]. This diversity in crystal structures seemed to arise from the participation of the anion accompanying Cd " " in the structure. The chiral MOF prepared from nitrate acts as an efficient heterogeneous catalyst for the room-temperature asymmetric addition of diethylzinc to a series of aromatic aldehydes, with ee values up to 90% at 100% substrate conversion. Conversely, the MOFs derived from the perchlorate salt were inactive under the same conditions. 

R)-2,2 -Dihydroxy-1,1 -binaphthyl [3] was examined in the O-H stretching region and from 950 to 1700 cm h For (IR, 5R, 6R)-(-)-spiro[4.4]nonane-1,6-diol [4], the theoretical VCD spectra were produced using vibronic coupling theory at the 6-3IG level. A comparison of the crystal structure of the ketal of the compound with optically pure (+)-(5(2-cholestan-3-one confirmed the results of the VCD determination. 

Mashima K, Nakamura T, Matsuo Y, Tani K. Convenient synthesis of anionic dinuclear ruthenium(ll) complexes [NR2H2] [ RuCl(diphosphine) 2(p.-Cl)3] [diphosphine = 2,2 -bis(diphenylphosphino)-l,l -binaphthyl, 2,2 -bis(di (p-tolyl)phosphino)-l,l -binaphthyl, and l,2-bis(diphenyl-phosphino)benzene] crystal structure of [NEt2H2][ RuCl... 

It is possible to translate the symbolism of the scissors and its basic structure into the field of molecules (cf. Fig. 11 b). Indeed, the scissor-shaped bulky binaphthyl compound equipped with two appending carboxy groups 1 (l,l -binaphthyl-2,2 -di-carboxylic acid, Fig. 11 c), as mentioned at the beginning (Sect. 1), strictly meets the general structure of an assumed coordinatoclathrate host (cf. Fig. 7). Also, the compound is in keeping with the considerations on an expectedly favorable lattice build-up (see Sect. 3.1). For checking, the crystal inclusion properties of 1 were studied in detail2). 

The structure of the parent compound 43 of the 1,1 -binaphthyl host family has been determined many times in independent laboratories and in different (racemic and resolved) crystal forms 60,61,72,73). A common feature of both types of structure is that molecules of 43 form helices. Lateral contacts between such helices play an important role in the respective crystals. These spatial arrangements also emphasize the importance of the question concerning the presence of alpha or beta substituents positioning as mentioned earlier 28 ... 

The tautomer 82c of 3-methylimidazole, however, was found in the 1 1 complex with rac-17. X-ray structure analysis of the above inclusion complex showed that molecules of 82c act as hydrogen-bond donors and acceptors between two dimeric assemblies of binaphthyl molecules (Scheme 2). Methyl groups are located in the vicinity of the dimeric host. However, steric hindrance of this methyl group is less important for the energetics of crystal construction than formation of two hydrogen bonds. 

The keto-enol equilibrium of the 1,3-diketones has been the subject of intensive studies using various physical techniques and theoretical calculations [78-80], Recently, X-ray crystal analysis of acetylacetone (83) was carried out at 110 K, and it was found that it exists as an equilibrium mixture of the two enol forms 83b and 83c [81]. Room-temperature studies show an acetylacetone molecule with the enolic H-atom centrally positioned, which can be attributed to the dynamically averaged structure 83d. Application of a crystal engineering technique showed that a 1 1 inclusion complex of83 can be formed with l,l/-binaphthyl-2,2/-dicarboxylic acid in which the enol form is stabilized by a notably short intramolecular hydrogen bond [82],... 

Fujiwara, T., Tanaka, N., Ooshita, R., Hino, R., Mori, K., and Toda, F. (1990) Crystal and Molecular Structure of the Crystalline Host-Guest Complex between (R)-(+)-2,2 -Dihydroxy-l,l -binaphthyl and (5)-(-)-(Ethyl m-Tolyl Selenoxide), Bull. Chem. Soc. Jpn., 63, 249-251. 

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