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Synthesis of Phosphane Oxide Bridged Bis- and Triscatechol

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Synthesis of Phosphane Oxide Bridged Bis- and Triscatechol http://www.paper.edu.cn PAPER 3037 Synthesis of Phosphane Oxide Bridged Bis- and Triscatechol Derivatives SynthesisMarkus of Phosphane Oxide Bridged Bis- and Triscatechol Derivatives Albrecht,*a Yun Songa,b a Institut für Organische Chemie, RWTH Aachen, Landoltweg 1, 52074 Aachen, Germany Fax +49(241)8094678; E-mail: [email protected] b College of Pharmaceuticals & Biotechnology, Tianjin University, Tianjin 300072, P. R. of China Received 17 May 2006; revised 18 June 2006 In our previous work, a series of bis- and triscatechol Abstract: Linear biscatechols and triangular triscatechols possess- ing spacers containing phosphane oxide were synthesized. For this, ligands 1 and 2 (Figure 1) with central carbon or nitrogen the central phosphorus was introduced by the reaction of active or- atoms have been synthesized. Systematic investigations ganometallic intermediates with either dichlorophenylphosphane or of the binding behavior of these ligands with various met- phosphorus trichloride/phosphoryl chloride. In the final steps, the al ions as well as the structural analysis of the resulting methyl ethers at the veratrol units were cleaved by boron tribromide complexes indicated that the structures of the supramolec- to afford the free phosphane oxide catechol derivatives, which in ular aggregates mainly depend on the geometry of the metal-directed self-assembly processes would lead to helical or tet- ligands.7 To further understand the influence of slight al- rahedral supramolecular aggregates. terations of the central atoms on the structure of the aggre- Key words: phosphane oxide, amides, catechol, ligands, Suzuki gates and to elucidate the general assembly mechanisms, coupling we now introduce phosphane oxide as the central unit in- stead of carbon or nitrogen, and prepared a series of linear and triangular bis- and triscatechol ligands. This work is The metal-directed self-assembly process of linear or tri- expected to open up a new approach for the design of angular catechol ligands can lead to helicate-type dinucle- helicate-type complexes and molecular containers with 1 2 ar complexes or to supramolecular tetrahedra. The functionalities introduced in the ‘wall’ of the containers.8 internal cavity of the resulting aggregates allows them to act as ‘molecular containers’ with certain reactive func- tionalities.3 As a fascinating kind of ‘reactors’, molecular Linear Dicatechols 4 containers can stabilize reactive intermediates, promote In earlier studies, we showed that linear biscatechol 1 5 chemical reactions, and enhance selectivities of intra- or (Figure 1), with a methylene unit providing the central 6 intermolecular reactions through accommodation of carbon atom, can assemble with titanium(IV) ions in the guest molecules. Therefore, the design of functionalized presence of sodium or lithium cations to form triple- ligands which can assemble to functional molecular con- stranded meso-helicates.7a tainers is currently one of the most challenging topics in supramolecular chemistry. In the present work, we substituted the methylene unit of 1 by a phosphoryl group, to obtain the linear biscatechol 3 (Scheme 1). Ligand 3 was prepared from veratrole (4), OH HO which was ortho-metalated with butyllithium (Scheme 1). Transmetalation to form the copper(I) species 5 was fol- OH HO H lowed by coupling with dichlorophenylphosphane; subse- C H N quent oxidation with 30% hydrogen peroxide afforded phosphane oxide 6. Deprotection with boron tribromide HO 2 led to the free ligand 3. OH 1 N 1. n-BuLi, OMe TMEDA 1. PhPCl2 CuLi 2. H O 2 2. CuI 2 2 N OH N OMe 12% OH 4 MeO OMe 2 OH 5 OH OMe OH Figure 1 Structures of bis- and triscatechol ligands 1 and 2 with BBr3 central carbon or nitrogen atoms OMe OMe OH OH O 92% O MeO P HO P 6 SYNTHESIS 2006, No. 18, pp 3037–3042xx.xx.2006 3 Advanced online publication: 15.08.2006 Scheme 1 Preparation of linear biscatechol 3 with a phosphoryl DOI: 10.1055/s-2006-950185; Art ID: Z09806SS group as the central unit © Georg Thieme Verlag Stuttgart · New York 转载 中国科技论文在线 http://www.paper.edu.cn 3038 M. Albrecht, Y. Song PAPER To separate the two catechol units by a longer spacer, we here, analogue 14, in which the central triangular unit is prepared compound 7 from 4-bromoaniline (8) by a six- substituted by a phosphoryl group, was prepared step reaction sequence (Scheme 2). The amine group of 4- (Scheme 3). Triscatechol 14 was prepared by procedures bromoaniline (8) was first protected by the addition of similar to those employed in the synthesis of ligand 7. In hexane-2,5-dione.9 The organometallic species formed by the first step, either phosphorus trichloride (followed by the reaction of protected aniline 9 with magnesium or bu- oxidation with hydrogen peroxide) or phosphoryl chloride tyllithium subsequently reacted with dichlorophenylphos- could be coupled with three equivalents of the organolith- phane, and oxidation by 30% hydrogen peroxide ium reagent obtained from protected aniline 9. The reac- followed. For this reaction step, we found that butyllithi- tion afforded phosphane oxide 15, which was deprotected um in dry diethyl ether gives more of the active with hydroxylamine hydrochloride to yield triaminophen- organometallic intermediate of 9 than magnesium in tetra- yl phosphane oxide 16, for which we had developed a re- hydrofuran can, to give phosphane oxide 10 in 76% yield liable synthetic procedure.12 This building block could be instead of 14%. After cleavage of the protected pyrrole also of interest as a ligand for catalysis or for materials sci- groups of 10 with hydroxylamine hydrochloride, the di- ence. Three equivalents of 2,3-dimethoxybenzoyl chlo- amino derivative 11 was acylated by addition of 2,3- ride (12) were coupled with phosphane oxide 16 in the dimethoxybenzoyl chloride (12). Finally, removal of the presence of O-benzotriazol-1-yl-N,N,N¢,N¢-tetramethyl- methoxy groups of derivative 13 by boron tribromide uronium hexafluorophosphate (HBTU) to yield 17, whose gave ligand 7 in 95% yield (Scheme 2). deprotection gave ligand 14. Triangular Triscatechols 1. n-BuLi Triangular catechol amides similar to imine 2 were pre- 2. PCl3 N N 3. H2O2 10 11 HONH Cl, pared by us and by Raymond. In the study presented 30% 3 Et3N, H2O 1. n-BuLi 1. Mg, THF 43% O 2. POCl3 2. PhPCl2 O 36% 3. H2O2 9 P N 14% Br O toluene N N NH2 15 91% 1. n-BuLi 2. PhPCl2 3. H O Br 2 2 9 76% OMe 8 O MeO Br MeO H OMe HN N COCl NH2 NH2 N OMe O P HONH3Cl, 12 O Et3N, H2O OMe 12, HBTU BBr3 O 63% O P 42% 90% O P 60% P O NH H2N NH2 17 H2N N 16 MeO 11 10 MeO OMe OH OH OMe O HO OH HO H HN O OH HN N HN O BBr3 O P 95% O O 14 P O O P O N O NH H N H OMe 13 HO OH 7 OMe OH HO Scheme 2 Preparation of linear biscatechol 7 with a phosphoryl Scheme 3 Synthesis of triscatechol amide 14 via phosphane oxide group in the center and with long spacers between the catechol units 16 as a key intermediate Synthesis 2006, No. 18, 3037–3042 © Thieme Stuttgart · New York 中国科技论文在线 http://www.paper.edu.cn PAPER Synthesis of Phosphane Oxide Bridged Bis- and Triscatechol Derivatives 3039 Scheme 4 illustrates the synthetic route to an alternative 1H, 31P, and 13C NMR spectra were recorded on a Varian Inova 400 triscatechol 18, in which a purely carbon skeleton con- spectrometer. FT-IR spectra were recorded on a Bruker IFS spec- nects the ligand units to the phosphoryl center. 1,4-Dibro- trometer (KBr or neat). Mass spectra (EI, 70 eV; FAB) were mea- 19 sured on a Finnigan MAT 95 or 212 mass spectrometer. Elemental mobenzene was metalated with butyllithium and then analyses were obtained with a Heraeus CHNO-Rapid analyzer. reacted with phosphoryl chloride or phosphorus trichlo- Melting points were determined on a Büchi B-540 apparatus and are ride/hydrogen peroxide. The thus obtained tris(4-bro- uncorrected. For organometallic reactions, the reaction flasks were mophenyl)phosphane oxide (20) was coupled with (2,3- flame-dried and the reactions were performed under an atmosphere dimethoxyphenyl)boronic acid (21) in a Suzuki cross- of dry N2. coupling reaction13 to afford hexamethoxy derivative 22. Removal of the methoxy protecting groups of precursor Bis(2,3-dimethoxyphenyl)(phenyl)phosphane Oxide (6) A 1.6 M soln of n-BuLi in hexane (5.6 mL, 8.96 mmol) was added 22 by boron tribromide smoothly gave triscatechol ligand to 1,2-dimethoxybenzene (4; 1.2 g, 8.7 mmol) and TMEDA (1.2 18. mL, 7.95 mmol) in dry Et2O (20 mL). After being stirred for 3 h at r.t., the mixture was added dropwise to a rapidly stirring slurry of HO OH CuI (835.0 mg, 4.4 mmol) in anhyd THF (25 mL) at –78 °C. The B resulting mixture was stirred at –78 °C for 15 min. PhPCl2 (780.0 OMe 1. n-BuLi Br mg, 4.4 mmol) and a few drops of HMPA were added. The mixture Br 2. POCl3 was allowed to warm to r.t. and was washed with sat. aq NH4Cl. Af- × 19% OMe ter the aqueous phase had been extracted with Et2O (3 30 mL), the 21 combined organic layer was concentrated (to 30 mL), and 30% 1. n-BuLi H O (3.0 mL) was added. After the mixture had refluxed for 4 h, 2. PCl3 O Suzuki, 65% 2 2 P 3. H2O2 the solvent was removed and the residue was dissolved in EtOAc Br 57% (30 mL).
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