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Search for "axial chirality" in Full Text gives 32 result(s) in Beilstein Journal of Organic Chemistry.
Homolytic substitution at phosphorus for C–P bond formation in organic synthesis
- Hideki Yorimitsu
Beilstein J. Org. Chem. 2013, 9, 1269–1277, doi:10.3762/bjoc.9.143
- phosphorus. Plausible mechanism of radical phosphination (Si = (Me3Si)3Si). Stereoselective phosphination leading to (S,S)-aminophosphine derivative. Phosphination with retention of axial chirality. Chemodivergent phosphination. Bis(phosphoryl)-bridged biphenyls by radical phosphination. Bis(phosphoryl
Graphical Abstract
Scheme 1: Representative C–P bond-forming reactions.
Scheme 2: General equation of homolytic substitution.
Scheme 3: Addition of diphenyl(triphenylstannyl)phosphine.
Scheme 4: Addition of diphenyl(trimethylstannyl)phosphine.
Scheme 5: Plausible mechanism of addition of R3Sn–PPh2.
Scheme 6: Addition of tetraorganodiphosphines to phenylacetylene.
Scheme 7: Plausible mechanism of anti-diphosphination.
Scheme 8: Radical diphosphination for synthesizing fluorescent material.
Scheme 9: Mechanism of thiophosphination with diphenyl(organosulfanyl)phosphine.
Scheme 10: Thiophosphination with S-thiophosphinyl O-ethyl dithiocarbonate.
Scheme 11: Photoinduced selenophosphination of allenes.
Scheme 12: Photoinduced tellurophosphination.
Scheme 13: Decarboxylative phosphorylation of carboxylic acid derivatives.
Scheme 14: Plausible mechanism of decarboxylative phosphorylation.
Scheme 15: Radical phosphination of PTOC esters with white phosphorus.
Scheme 16: Plausible mechanism of radical phosphination (Si = (Me3Si)3Si).
Scheme 17: Stereoselective phosphination leading to (S,S)-aminophosphine derivative.
Figure 1: Calculated reaction profile of homolytic substitution between Ph• and Me3Sn–PPh2 at the B2-PLYP-D/T...
Scheme 18: Phosphination with retention of axial chirality.
Scheme 19: Chemodivergent phosphination.
Scheme 20: Bis(phosphoryl)-bridged biphenyls by radical phosphination.
Scheme 21: Bis(phosphoryl)-bridged ladder triphenylene by radical phosphination.
Scheme 22: Photoinduced phosphination of perfluoroalkyl iodides with tetraphenyldiphosphine.
Scheme 23: Ti(III)-mediated radical phosphination of organic bromides with white phosphorus.
Design and synthesis of quasi-diastereomeric molecules with unchanging central, regenerating axial and switchable helical chirality via cleavage and formation of Ni(II)–O and Ni(II)–N coordination bonds
- Vadim A. Soloshonok,
- José Luis Aceña,
- Hisanori Ueki and
- Jianlin Han
Beilstein J. Org. Chem. 2012, 8, 1920–1928, doi:10.3762/bjoc.8.223
- *) and (Ra*,Ph*,Rc*) occurs by intramolecular trans-coordination of Ni–NH and Ni–O bonds providing a basis for a chiral switch model. Keywords: axial chirality; central chirality; chiral switches; coordination bonds; functional materials; helical chirality; modular structural design; molecular devices
- concurrent and unidirectional motion of arms ED and AB is expected to have the following desired stereochemical consequences: Thus, the axial chirality on the arm CDE in 5 will disappear with simultaneous generation of a new chiral axis on the arm CBA in 6, of the same stereochemical sense. Next, this
- envisioned mode of transcoordination must proceed also with a loss and regeneration of helical chirality, but, in contrast to the loss/regeneration of axial chirality, with the inversion of the stereochemical sense, providing quasi-diastereomeric relationships between complexes 5 and 6 [26]. As one can
Graphical Abstract
Scheme 1: Previous design of diastereomeric molecules 2 and 3 with switchable chirality starting from achiral...
Scheme 2: General design of asymmetric pentadentate ligands 4 and chiroptically switchable quasi-diastereomer...
Scheme 3: Preparation of imino–carbonyl ligands 13 by desymmetrization of achiral carbonyl–carbonyl ligands 12...
Scheme 4: Preparation of complexes 14a,b and 15 by reactions of ligands 12 with glycine.
Figure 1: Crystallographic structure of complex 14a.
Scheme 5: Oxidation of enolates 16 and formation of complexes 19 and 20.
Figure 2: Crystallographic structure of complex 19.
The interplay of configuration and conformation in helical perylenequinones: Insights from chirality induction in liquid crystals and calculations
- Elisa Frezza,
- Silvia Pieraccini,
- Stefania Mazzini,
- Alberta Ferrarini and
- Gian Piero Spada
Beilstein J. Org. Chem. 2012, 8, 155–163, doi:10.3762/bjoc.8.16
- essentially determined by the axial chirality (helicity) of the core of the perylenequinones. Keywords: chirality; conformational analysis; DFT calculations; helical twisting power; nematic liquid crystals; Introduction The phenomenon of chiral induction in nematic mesophases has been known for a long time
- the determination of the absolute configuration [2][3][5][6][12][13][14][15][16][17][18][19][20][21][22][23][24]. In fact, this technique has been fruitfully applied to different classes of systems, possessing either stereogenic centers or axial chirality. In this work, chirality induction in liquid
- ) [27], shown in Figure 1. They have the same stereochemical features: Two bulky methoxy groups or a strained seven-membered ring in positions 6 and 7, two side chains in positions 1 and 12 and a nonplanar helical shape. The helicity generates axial chirality, which, when associated with the presence of
Graphical Abstract
Figure 1: Chemical structure of the helical perylenequinones under investigation: Cercosporin (1) and phleich...
Figure 2: Newman projections of the conformational states of the side chain linked at C1 of cercosporin (1), ...
Figure 3: “Propeller” (left) and “double butterfly” geometry (right) of the g+ g+ conformer of 1, as obtained...
Figure 4: Optimized geometry of all conformers of 1 (upper half) and 2 (lower half), obtained at the DFT/M06-...
Figure 5: Chirality parameter Q (diamonds) and probability distribution (bars), calculated for all conformers...
Bromine–lithium exchange: An efficient tool in the modular construction of biaryl ligands
- Laurence Bonnafoux,
- Frédéric R. Leroux and
- Françoise Colobert
Beilstein J. Org. Chem. 2011, 7, 1278–1287, doi:10.3762/bjoc.7.148
- . Catalytic studies as well as the control of biaryl axial chirality are currently underway and will be reported in due course. Modular synthesis of bis(diarylphosphino)-, bis(dialkylphosphino)- and dialkyl(diaryl)phosphinobiphenyls as well as monophosphinobiphenyls by means of polar organometallic chemistry
Graphical Abstract
Figure 1: Modular synthesis of bis(diarylphosphino)-, bis(dialkylphosphino)- and dialkyl(diaryl)phosphinobiph...
Figure 2: ARYNE coupling.
Scheme 1: Functionalization of 2,2',6-tribromobiphenyl (1a) by regioselective bromine–lithium exchange.
Scheme 2: Functionalization of 2,2'-dibromobiphenyls (1b–e) by regioselective bromine–lithium exchange.
Figure 3: General access to biaryl mono- and diphosphine ligands; (Cy = cyclohexyl).
Scheme 3: Synthesis of monophosphines 3; (Cy = cyclohexyl).
Figure 4: Molecular structure of compound 3a (crystallized from ethyl acetate/hexane) [74].
Scheme 4: Preparation of mixed dialkyl(diaryl)phosphinobiphenyls 5 via successive bromine–lithium exchange.
Scheme 5: Stepwise bromine–lithium exchange on 1c.
Cationic gold(I) axially chiral biaryl bisphosphine complex-catalyzed atropselective synthesis of heterobiaryls
- Tetsuro Shibuya,
- Kyosuke Nakamura and
- Ken Tanaka
Beilstein J. Org. Chem. 2011, 7, 944–950, doi:10.3762/bjoc.7.105
- complex catalyzes the atropselective intramolecular hydroarylation of alkynes leading to enantioenriched axially chiral 4-aryl-2-quinolinones and 4-arylcoumarins with up to 61% ee. Keywords: asymmetric catalysis; axial chirality; gold; heterobiaryls; hydroarylation; Introduction Atropselective biaryl
Graphical Abstract
Scheme 1: Cationic gold(I)/PPh3-complex catalyzed intramolecular hydroalkenylation of alkynes.
Scheme 2: Cationic palladium(II)/(S)-xyl-Segphos-complex catalyzed atropselective intramolecular hydroalkenyl...
Scheme 3: Cationic palladium(II)/(S)-xyl-H8-BINAP complex-catalyzed atropselective intramolecular hydroarylat...
Figure 1: Structures of axially chiral biaryl bisphosphine ligands.
Scheme 4: Cationic gold(I)/(R)-DTBM-Segphos-complex catalyzed atropselective intramolecular hydroarylation of...
Molecular recognition of organic ammonium ions in solution using synthetic receptors
- Andreas Späth and
- Burkhard König
Beilstein J. Org. Chem. 2010, 6, No. 32, doi:10.3762/bjoc.6.32
Graphical Abstract
Figure 1: Biologically important amines and quaternary ammonium salts: histamine (1), dopamine (2) and acetyl...
Figure 2: Crown ether 18-crown-6.
Figure 3: Conformations of 18-crown-6 (4) in solvents of different polarity.
Figure 4: Binding topologies of the ammonium ion depending on the crown ring size.
Figure 5: A “pseudorotaxane” structure consisting of 24-crown-8 and a secondary ammonium ion (5); R = Ph.
Figure 6: Typical examples of azacrown ethers, cryptands and related aza macrocycles.
Figure 7: Binding of ammonium to azacrown ethers and cryptands [111-113].
Figure 8: A 19-crown-6-ether with decalino blocking groups (11) and a thiazole-dibenzo-18-crown-6-ether (12).
Figure 9: 1,3-Bis(6-oxopyridazin-1-yl)propane derivatives 13 and 14 by Campayo et al.
Figure 10: Fluorescent azacrown-PET-sensors based on coumarin.
Figure 11: Two different pyridino-cryptands (17 and 18) compared to a pyridino-crown (19); chiral ammonium ion...
Figure 12: Pyridino-18-crown-6 ligand (21), a similar acridino-18-crown-6 ligand (22) and a structurally relat...
Figure 13: Ciral pyridine-azacrown ether receptors 24.
Figure 14: Chiral 15-crown-5 receptors 26 and an analogue 18-crown-6 ligand 27 derived from amino alcohols.
Figure 15: C2-symmetric chiral 18-crown-6 amino alcohol derivatives 28 and related macrocycles.
Figure 16: Macrocycles with diamide-diester groups (30).
Figure 17: C2-symmetric chiral aza-18-crown-6 ethers (31) with phenethylamine residues.
Figure 18: Chiral C-pivot p-methoxy-phenoxy-lariat ethers.
Figure 19: Chiral lariat crown ether 34.
Figure 20: Sucrose-based chiral crown ether receptors 36.
Figure 21: Permethylated fructooligosaccharide 37 showing induced-fit chiral recognition.
Figure 22: Biphenanthryl-18-crown-6 derivative 38.
Figure 23: Chiral lariat crown ethers derived from binol by Fuji et al.
Figure 24: Chiral phenolic crown ether 41 with “aryl chiral barriers” and guest amines.
Figure 25: Chiral bis-crown receptor 43 with a meso-ternaphthalene backbone.
Figure 26: Chromogenic pH-dependent bis-crown chemosensor 44 for diamines.
Figure 27: Triamine guests for binding to receptor 44.
Figure 28: Chiral bis-crown phenolphthalein chemosensors 46.
Figure 29: Crown ether amino acid 47.
Figure 30: Luminescent receptor 48 for bis-alkylammonium guests.
Figure 31: Luminescent CEAA (49a), a bis-CEAA receptor for amino acids (49b) and the structure of lysine bindi...
Figure 32: Luminescent CEAA tripeptide for binding small peptides.
Figure 33: Bis crown ether 51a self assembles co-operatively with C60-ammonium ion 51b.
Figure 34: Triptycene-based macrotricyclic dibenzo-[24]-crown-8 ether host 52 and guests.
Figure 35: Copper imido diacetic acid azacrown receptor 53a and the suggested His-Lys binding motif; a copper ...
Figure 36: Urea (54) and thiourea (55) benzo crown receptor for transport and extraction of amino acids.
Figure 37: Crown pyryliums ion receptors 56 for amino acids.
Figure 38: Ditopic sulfonamide bridged crown ether receptor 57.
Figure 39: Luminescent peptide receptor 58.
Figure 40: Luminescent receptor 59 for the detection of D-glucosamine hydrochloride in water/ethanol and lumin...
Figure 41: Guanidinium azacrown receptor 61 for simple amino acids and ditopic receptor 62 with crown ether an...
Figure 42: Chiral bicyclic guanidinium azacrown receptor 63 and similar receptor 64 for the enantioselective t...
Figure 43: Receptors for zwitterionic species based on luminescent CEAAs.
Figure 44: 1,10-Azacrown ethers with sugar podand arms and the anticancer agent busulfan.
Figure 45: Benzo-18-crown-6 modified β-cyclodextrin 69 and β-cyclodextrin functionalized with diaza-18-crown-6...
Figure 46: Receptors for colorimetric detection of primary and secondary ammonium ions.
Figure 47: Porphyrine-crown-receptors 72.
Figure 48: Porphyrin-crown ether conjugate 73 and fullerene-ammonium ion guest 74.
Figure 49: Calix[4]arene (75a), homooxocalix[4]arene (75b) and resorcin[4]arene (75c) compared (R = H, alkyl c...
Figure 50: Calix[4]arene and ammonium ion guest (R = H, alkyl, OAcyl etc.), possible binding sites; A: co-ordi...
Figure 51: Typical guests for studies with calixarenes and related molecules.
Figure 52: Lower rim modified p-tert-butylcalix[5]arenes 82.
Figure 53: The first example of a water soluble calixarene.
Figure 54: Sulfonated water soluble calix[n]arenes that bind ammonium ions.
Figure 55: Displacement assay for acetylcholine (3) with a sulfonato-calix[6]arene (84b).
Figure 56: Amino acid inclusion in p-sulfonatocalix[4]arene (84a).
Figure 57: Calixarene receptor family 86 with upper and lower rim functionalization.
Figure 58: Calix[6]arenes 87 with one carboxylic acid functionality.
Figure 59: Sulfonated calix[n]arenes with mono-substitution at the lower rim systematically studied on their r...
Figure 60: Cyclotetrachromotropylene host (91) and its binding to lysine (81c).
Figure 61: Calixarenes 92 and 93 with phosphonic acids groups.
Figure 62: Calix[4]arene tetraphosphonic acid (94a) and a double bridged analogue (94b).
Figure 63: Calix[4]arene tetraphosphonic acid ester (92c) for surface recognition experiments.
Figure 64: Calixarene receptors 95 with α-aminophosphonate groups.
Figure 65: A bridged homocalix[3]arene 95 and a distally bridged homocalix[4]crown 96.
Figure 66: Homocalix[3]arene ammonium ion receptor 97a and the Reichardt’s dye (97b) for colorimetric assays.
Figure 67: Chromogenic diazo-bridged calix[4]arene 98.
Figure 68: Calixarene receptor 99 by Huang et al.
Figure 69: Calixarenes 100 reported by Parisi et al.
Figure 70: Guest molecules for inclusion in calixarenes 100: DAP × 2 HCl (101a), APA (101b) and Lys-OMe × 2 HC...
Figure 71: Different N-linked peptido-calixarenes open and with glycol chain bridges.
Figure 72: (S)-1,1′-Bi-2-naphthol calixarene derivative 104 published by Kubo et al.
Figure 73: A chiral ammonium-ion receptor 105 based on the calix[4]arene skeleton.
Figure 74: R-/S-phenylalaninol functionalized calix[6]arenes 106a and 106b.
Figure 75: Capped homocalix[3]arene ammonium ion receptor 107.
Figure 76: Two C3 symmetric capped calix[6]arenes 108 and 109.
Figure 77: Phosphorous-containing rigidified calix[6]arene 110.
Figure 78: Calix[6]azacryptand 111.
Figure 79: Further substituted calix[6]azacryptands 112.
Figure 80: Resorcin[4]arene (75c) and the cavitands (113).
Figure 81: Tetrasulfonatomethylcalix[4]resorcinarene (114).
Figure 82: Resorcin[4]arenes (115a/b) and pyrogallo[4]arenes (115c, 116).
Figure 83: Displacement assay for acetylcholine (3) with tetracyanoresorcin[4]arene (117).
Figure 84: Tetramethoxy resorcinarene mono-crown-5 (118).
Figure 85: Components of a resorcinarene based displacement assay for ammonium ions.
Figure 86: Chiral basket resorcin[4]arenas 121.
Figure 87: Resorcinarenes with deeper cavitand structure (122).
Figure 88: Resorcinarene with partially open deeper cavitand structure (123).
Figure 89: Water-stabilized deep cavitands with partially structure (124, 125).
Figure 90: Charged cavitands 126 for tetralkylammonium ions.
Figure 91: Ditopic calix[4]arene receptor 127 capped with glycol chains.
Figure 92: A calix[5]arene dimer for diammonium salt recognition.
Figure 93: Calixarene parts 92c and 129 for the formation molecular capsules.
Figure 94: Encapsulation of a quaternary ammonium cation by two resorcin[4]arene molecules (NMe4+@[75c]2 × Cl−...
Figure 95: Encapsulation of a quaternary ammonium cation by six resorcin[4]arene molecules (NMe3D+@[130]6 × Cl−...
Figure 96: Structure and schematic of cucurbit[6]uril (CB[6], 131a).
Figure 97: Cyclohexanocucurbit[6]uril (CB′[6], 132) and the guest molecule spermine (133).
Figure 98: α,α,δ,δ-Tetramethylcucurbit[6]uril (134).
Figure 99: Structure of the cucurbituril-phthalhydrazide analogue 135.
Figure 100: Organic cavities for the displacement assay for amine differentiation.
Figure 101: Displacement assay methodology for diammonium- and related guests involving cucurbiturils and some ...
Figure 102: Nor-seco-Cucurbituril (±)-bis-ns-CB[6] (140) and guest molecules.
Figure 103: The cucurbit[6]uril based complexes 141 for chiral discrimination.
Figure 104: Cucurbit[7]uril (131c) and its ferrocene guests (142) opposed.
Figure 105: Cucurbit[7]uril (131c) guest inclusion and representative guests.
Figure 106: Cucurbit[7]uril (131c) binding to succinylcholine (145) and different bis-ammonium and bis-phosphon...
Figure 107: Paraquat-cucurbit[8]uril complex 149.
Figure 108: Gluconuril-based ammonium receptors 150.
Figure 109: Examples of clefts (151a), tweezers (151b, 151c, 151d) and clips (151e).
Figure 110: Kemp’s triacid (152a), on example of Rebek’s receptors (152b) and guests.
Figure 111: Amino acid receptor (154) by Rebek et al.
Figure 112: Hexagonal lattice designed hosts by Bell et al.
Figure 113: Bell’s amidinium receptor (156) and the amidinium ion (157).
Figure 114: Aromatic phosphonic acids.
Figure 115: Xylene phosphonates 159 and 160a/b for recognition of amines and amino alcohols.
Figure 116: Bisphosphonate recognition motif 161 for a colorimetric assay with alizarin complexone (163) for ca...
Figure 117: Bisphosphonate/phosphate clip 164 and bisphosphonate cleft 165.
Figure 118: N-Methylpyrazine 166a, N-methylnicotinamide iodide (166b) and NAD+ (166c).
Figure 119: Bisphosphate cavitands.
Figure 120: Bisphosphonate 167 of Schrader and Finocchiaro.
Figure 121: Tweezer 168 for noradrenaline (80b).
Figure 122: Different tripods and heparin (170).
Figure 123: Squaramide based receptors 172.
Figure 124: Cage like NH4+ receptor 173 of Kim et al.
Figure 125: Ammonium receptors 174 of Chin et al.
Figure 126: 2-Oxazolin-based ammonium receptors 175a–d and 176 by Ahn et al.
Figure 127: Racemic guest molecules 177.
Figure 128: Tripods based on a imidazole containing macrocycle (178) and the guest molecules employed in the st...
Figure 129: Ammonium ion receptor 180.
Figure 130: Tetraoxa[3.3.3.3]paracyclophanes 181 and a cyclophanic tetraester (182).
Figure 131: Peptidic bridged paraquat-cyclophane.
Figure 132: Shape-selective noradrenaline host.
Figure 133: Receptor 185 for binding of noradrenaline on surface layers from Schrader et al.
Figure 134: Tetraphosphonate receptor for binding of noradrenaline.
Figure 135: Tetraphosphonate 187 of Schrader and Finocchiaro.
Figure 136: Zinc-Porphyrin ammonium-ion receptors 188 and 189 of Mizutani et al.
Figure 137: Zinc porphyrin receptor 190.
Figure 138: Zinc porphyrin receptors 191 capable of amino acid binding.
Figure 139: Zinc-porphyrins with amino acid side chains for stereoinduction.
Figure 140: Bis-zinc-bis-porphyrin based on Tröger’s base 193.
Figure 141: BINAP-zinc-prophyrin derivative 194 and it’s guests.
Figure 142: Bisaryl-linked-zinc-porphyrin receptors.
Figure 143: Bis-zinc-porphyrin 199 for diamine recognition and guests.
Figure 144: Bis-zinc-porphyrin crown ether 201.
Figure 145: Bis-zinc-porphyrin 202 for stereodiscrimination (L = large substituent; S = small substituent).
Figure 146: Bis-zinc-porphyrin[3]rotaxane and its copper complex and guests.
Figure 147: Dien-bipyridyl ligand 206 for co-ordination of two metal atoms.
Figure 148: The ligand and corresponding tetradentate co-complex 207 serving as enantioselective receptor for a...
Figure 149: Bis(oxazoline)–copper(II) complex 208 for the recognition of amino acids in aqueous solution.
Figure 150: Zinc-salen-complexes 209 for the recognition tertiary amines.
Figure 151: Bis(oxazoline)–copper(II) 211 for the recognition of amino acids in aqueous solution.
Figure 152: Zn(II)-complex of a C2 terpyridine crown ether.
Figure 153: Displacement assay and receptor for aspartate over glutamate.
Figure 154: Chiral complex 214 for a colorimetric displacement assay for amino acids.
Figure 155: Metal complex receptor 215 with tripeptide side arms.
Figure 156: A sandwich complex 216 and its displaceable dye 217.
Figure 157: Lanthanide complexes 218–220 for amino acid recognition.
Figure 158: Nonactin (221), valinomycin (222) and vancomycin (223).
Figure 159: Monesin (224a) and a chiral analogue for enantiodiscrimination of ammonium guests (224b).
Figure 160: Chiral podands (226) compared to pentaglyme-dimethylether (225) and 18-crown-6 (4).
Figure 161: Lasalocid A (228).
Figure 162: Lasalocid derivatives (230) of Sessler et al.
Figure 163: The Coporphyrin I tetraanion (231).
Figure 164: Linear and cyclic peptides for ammonium ion recognition.
Figure 165: Cyclic and bicyclic depsipeptides for ammonium ion recognition.
Figure 166: α-Cyclodextrin (136a) and novocaine (236).
Figure 167: Helical diol receptor 237 by Reetz and Sostmann.
Figure 168: Ammonium binding spherand by Cram et al. (238a) and the cyclic[6]metaphenylacetylene 238b in compar...
Figure 169: Receptor for peptide backbone and ammonium binding (239).
Figure 170: Anion sensor principle with 3-hydroxy-2-naphthanilide of Jiang et al.
Figure 171: 7-bromo-3-hydroxy-N-(2-hydroxyphenyl)naphthalene 2-carboxamide (241) and its amine binding.
Figure 172: Naturally occurring catechins with affinity to quaternary ammonium ions.
Figure 173: Spiropyran (244) and merocyanine form (244a) of the amino acid receptors of Fuji et al.
Figure 174: Coumarin aldehyde (245) and its iminium species with amino acid bound (245a) by Glass et al.
Figure 175: Coumarin aldehyde appended with boronic acid.
Figure 176: Quinolone aldehyde dimers by Glass et al.
Figure 177: Chromogenic ammonium ion receptors with trifluoroacetophenone recognition motifs.
Figure 178: Chromogenic ammonium ion receptor with trifluoroacetophenone recognition motif bound on different m...
Control of asymmetric biaryl conformations with terpenol moieties: Syntheses, structures and energetics of new enantiopure C2- symmetric diols
- Y. Alpagut,
- B. Goldfuss and
- J.-M. Neudörfl
Beilstein J. Org. Chem. 2008, 4, No. 25, doi:10.3762/bjoc.4.25
- : chiral diols; hydrogen bonds; axial chirality; terpenes; Introduction Enantiopure biaryl systems with flexible chiral axes are widespread, e.g. in pharmacological natural products or as ligands in enantioselective catalyses [1]. Chelating C2-symmetric diols such as BINOLs [2][3][4] and TADDOLs [5][6
Graphical Abstract
Scheme 1: Atropisomeric BINOL and conformationally restricted, (−)-fenchone-based (M)-BIFOL.
Scheme 2: Syntheses of (M)-BIMOL, (P)-BIVOL, (P)-BICOL, and (P)-BIMEOL.
Figure 1: X-Ray crystal structure of (M)-BIMOL. An acetone molecule, binding to the external OH group, is omi...
Figure 2: X-Ray crystal structure of (P)-BIVOL. A water molecule, binding to the external OH group, is omitte...
Figure 3: X-Ray crystal structure of (P)-BICOL. A water molecule, binding to the external OH group, is omitte...
Figure 4: X-Ray crystal structure of (P)-BIMEOL. An ethanol molecule, binding to the external OH group, is om...
Figure 5: B3LYP/6-31++G**:AM1 optimized structure of (M)-BIMOL, Erel. = 0.0 kcal/mol.
Figure 6: B3LYP/6-31++G**:AM1 optimized structure of (P)-BIMOL, Erel. = 1.3 kcal/mol.
Figure 7: B3LYP/6-31++G**:AM1 optimized structure of (M)-BIVOL, Erel. = 5.1 kcal/mol.
Figure 8: B3LYP/6-31++G**:AM1 optimized structure of (P)-BIVOL, Erel. = 0.0 kcal/mol.
Figure 9: B3LYP/6-31++G**:AM1 optimized structure of (M)-BICOL, Erel. = 5.8 kcal/mol.
Figure 10: B3LYP/6-31++G**:AM1 optimized structure of (P)-BICOL, Erel. = 0.0 kcal/mol.
Figure 11: B3LYP/6-31++G**:AM1 optimized structure of (M)-BIMEOL, Erel. = 5.4 kcal/mol.
Figure 12: B3LYP/6-31++G**:AM1 optimized structure of (P)-BIMEOL, Erel. = 0.0 kcal/mol.
Scheme 3: Co-solvent adducts in the X-ray structures of (M)-BIMOL, (P)-BIVOL, (P)-BICOL, and (P)-BIMEOL.
