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1.
Yuji Takashima 《Tetrahedron》2010,66(1):197-2519
A general approach to the (S)- and (R)-isoflavans was invented, and efficiency of the method was demonstrated by the synthesis of (S)-equol ((S)-3), (R)-sativan ((R)-4), and (R)-vestitol ((R)-5). The key step is the allylic substitution of (S)-6a (Ar1=2,4-(MeO)2C6H3) and (R)-6b (Ar1=2,4-(BnO)2C6H3) with copper reagents derived from CuBr·Me2S and Ar2-MgBr (7a, Ar2=4-MeOC6H4; 7b, 2,4-(MeO)2C6H3; 7c, 2-MOMO-4-MeOC6H3), furnishing anti SN2′ products (R)-8a and (S)-8b,c with 93-97% chirality transfer in 60-75% yields. The olefinic part of the products was oxidatively cleaved and the Me and Bn groups on the Ar1 moieties was then removed. Finally, phenol bromide 9a and phenol alcohols 9b,c underwent cyclization with K2CO3 and the Mitsunobu reagent to afford (S)-3 and (R)-4 and -5, respectively.  相似文献   

2.
Four half-sandwich ruthenium(II) complexes [(η6-C6H6)Ru(L1-O)][PF6] (1), [(η6-C6H6)Ru(L2-O)][PF6] (2), [(η6-C6H6)Ru(L3-O)][PF6] (3), [(η6-C6H6)Ru(L4-O)][PF6] (4a), and [(η6-C6H6)Ru(L4-O)][BPh4] (4b) [L1-OH, 4-nitro-6-{[(2′-(pyridin-2-yl)ethyl)methylamino]methyl}-phenol; L2-OH, 2,4-di-tert-butyl-6-{[(2′-(pyridin-2-yl)ethyl)methylamino]methyl}-phenol; L3-OH, 2,4-di-tert-butyl-6-{[2′-((pyridin-2-yl)benzylamino)methyl}-phenol; L4-OH, 2,4-di-tert-butyl-6-{[(2′-imethylaminoethyl)methylamino]methyl}-phenol (L4-OH)], supported by a systematically varied series of tridentate phenolate-based pyridylalkylamine and alkylamine ligands are reported. The molecular structures of 1-3, 4a, and 4b have been elucidated in solution using 1H NMR spectroscopy and of 1, 3, and 4b in the solid state by X-ray crystallography. Notably, due to coordination by the ligands the Ru center assumes a chiral center and in turn the central amine nitrogen also becomes chiral. The 1H NMR spectra exhibit only one set of signals, suggesting that the reaction is completely diastereoselective [1: SRu,SN/RRu,RN; 2: RRu,RN/SRu,SN; 3: SRu,RN/RRu,SN; 4b: SRu,RN/RRu,SN]. The crystal packing in 1 and 3 is stabilized by C-HO interactions, in 4b no meaningful secondary interactions are observed. From the standpoint of generating phenoxyl radical, as investigated by cyclic voltammetry (CV), complex 1 is redox-inactive in MeCN solution. However, 2, 3, and 4a generate a one-electron oxidized phenoxyl radical coordinated species [2]2+, [3]2+, and [4a]2+, respectively. The radical species are characterized by CV, UV-Vis, and EPR spectroscopy. The stability of the radical species has been determined by measuring the decay constant (UV-Vis spectroscopy).  相似文献   

3.
This report describes the conversion of the neutral planar chiral arene-tethered complex [Ru(η61-Me2NC6H4C6H4PCy2)Cl2 (1), into [Ru(η6: η1-Me2NC6H4C6H4PCy2)(1,3-dibutylimidazol-2-ylidene)Cl]BF4 (2) via silver transmetallation. The cationic title complex is also chiral-at-metal, and forms stereoselectively as a result of the directing effect of the arene-tethered ligand. The structure in solution and in the solid state was examined; a puckered distortion of the η6-arene was noted in the crystal structure, along with a hindered rotation of the NHC in solution. As a comparison to the previously reported phosphine analogues, the dication derived from 2 was used to catalyze the asymmetric Diels-Alder reaction of methacrolein and cyclopentadiene.  相似文献   

4.
The mononuclear cations of the general formula [(η6-arene)RuCl(dpqMe2)]+ (dpqMe2 = 6,7-dimethyl-2,3-di(pyridine-2-yl)quinoxaline; arene = C6H6, 1; C6H5Me, 2; p-PriC6H4Me, 3; C6Me6, 4) as well as the dinuclear dications [(η6-arene)2Ru2Cl2(μ-dpqMe2)]2+ (arene = C6H6, 5; C6H5Me, 6; p-PriC6H4Me, 7; C6Me6, 8) have been synthesised from 6,7-dimethyl-2,3-di(pyridine-2-yl)quinoxaline (dpqMe2) and the corresponding chloro complexes [(η6-C6H6)Ru(μ-Cl)Cl]2, [(η6-C6H5Me)Ru(μ-Cl)Cl]2, [(η6-p-PriC6H4Me)Ru(μ-Cl)Cl]2 and [(η6-C6Me6)Ru(μ-Cl)Cl]2, respectively. The X-ray crystal structure analyses of [1][PF6], [3][PF6] and [6][PF6]2 reveal a typical piano-stool geometry around the metal centre; in the dinuclear complexes the two chloro ligands, with respect to each other, are found to be trans oriented.  相似文献   

5.
2,4,6-Triphenylpyrylium tetrafluoroborate (TPPBF4)-sensitized photoinduced electron-transfer (PET) reactions of 1,4-diaryl-2,3-dioxabicyclo[2.2.2]octanes 5 (a: Ar1 = Ar2 = p-MeOC6H4, b: Ar1 = Ar2 = p-MeC6H4, c: Ar1 = Ar2 = Ph) underwent novel fragmentation through their radical cations to give 1,4-diarylbutan-1,4-diones 6 accompanied by elimination of ethylene. On the other hand, 4-aryl-cyclohex-3-en-1-ones 7, p-substituted phenols 8, and 4-aryl-4-aryloxycyclohexanones 9 were produced through proton-catalyzed pathways when the PET reactions of 5 were performed in the absence of a certain base such as 2,6-di-tert-butylpyridine (DTBP). Particularly, the formation of 9 is consistent with the novel cationic rearrangement involving nucleophilic O-1,2-aryl shifts and C-1,4-aryl shifts.  相似文献   

6.
The chiral, terpenoid-substituted yttrocene [(η5-neomenthylCp)2Y{o-C6H4CH2NMe2}] (1) can be prepared via facile arene elimination starting from [Y(o-C6H4CH2NMe2)3]. Compound 1 retains a C1-symmetric structure in solution on the NMR time scale, due to tight binding of the amine donor. The (−)-phenylmenthyl-substituted complexes [(η5-(−)-phenylmenthylCp)2Y(μ-Cl)2Li(OEt2)2] (5) and [(η5-(−)-phenylmenthylCp)2YN(SiMe3)2] (6) were prepared via salt metathesis. Reaction of YCl3 with the planar chiral (1-neomenthylindenyl)lithium predominantly produced a single, C2-symmetric, racemic-like diastereomer. The X-ray crystal structure analysis confirmed that [(η5-(+)-NMInd)2Y(μ-Cl)2Li(Et2O)2] (7) represents the same p-S, p-S metallocene diastereomer and adopts a very similar conformation as observed by Erker in his zirconocene complexes. Complex 7 reacts with LiN(SiMe3)2 to form [(η5-(+)-NMInd)2YN(SiMe3)2] (8) with retention of configuration. Complexes 1, 6 and 8 showed moderate to good catalytic activity in asymmetric hydroamination/cyclizations of aminoalkenes, but enantioselectivities were limited to a maximum of 38% ee for the sterically most hindered catalyst 8. The indenyl complex 8 is prone to protolytic loss of an indenyl ligand at low (?0.5%) catalyst loading, if sterically undemanding aminoalkene substrates are applied.  相似文献   

7.
8.
Compounds of general formula Mo(η6-arene)(CO)3, arene=diphenyl, 1; 1,3,5-triphenylbenzene, 2; C6H5F, 3; C6H5CF3, 4, have been prepared in good yields by reacting fac-Mo(CO)3(DMF)3, DMF=N,N-dimethylformamide, with BF3 · OEt2 and the appropriate arene. The crystal and molecular structures of 1, 3, and 4, are reported. The dinuclear derivative Mo266-C6H5-C6H5)(CO)6, 5, was obtained by thermal reaction of Mo(η6-toluene)(CO)3 with Mo(η6-diphenyl)(CO)3. An electrochemical study has been performed on the new complexes, showing that the dimolybdenum complex undergoes a single two-electron reduction at about the same potential as the corresponding dichromium complex, the molybdenum dianion being less stable than the chromium analogue.  相似文献   

9.
A series of mono-cationic dinuclear half sandwich ruthenium, rhodium and iridium metal complexes have been synthesized using ((pyridin-2-yl)methylimino)nicotinamide (L1) and ((picolinamido)phenyl)picolinamide (L2) ligands: [(η6-arene)2Ru2(μ-L1)Cl3]+ (arene = C6H6, 1; p-iPrC6H4Me, 2; C6Me6, 3), [(η5-C5Me5)2M2(μ-L1)Cl3]+ (M = Rh, 4; Ir, 5), and [(η6-arene)2Ru2(μ-L2)(μ-Cl)]+ (arene = C6H6, 6; p-iPrC6H4Me, 7; C6Me6, 8), [(η5-C5Me5)2M2(μ-L2)Cl2]+ (M = Rh, 9; Ir, 10). All the complexes have been isolated as their hexafluorophosphate salts and fully characterized by use of a combination of NMR and IR spectroscopy. The solid state structure of three representatives 4, 6 and 9 has been determined by X-ray crystallographic studies. Interestingly, in the molecular structure of 4, the first metal is bonded to two nitrogen atoms whereas the second metal center is coordinated to only one nitrogen atom with two terminal chloride ligands. Fascinatingly in the case of the complexes with the symmetrical ligand L2, both ruthenium centers having η6-arene groups are bonded to nitrogen atoms with a bridging chloride atom between the two metal centers, whereas the metals with η5-Cp∗ groups are bonded to the ligand N,O and N,N fashion.  相似文献   

10.
Planar chiral alkenylferrocene phosphanes, viz. (Sp)-[Fe(η5-C5H3-1-PPh2-2-CHCR2)(η5-C5H5)] (R = H, (Sp)-2; Ph, (Sp)-5) and (Sp)-[Fe(η5-C5H3-1-PPh2-2-(E)-CHCHR)(η5-C5H5)] (R = Ph, (Sp)-3; C(O)CH3, (Sp)-6; and CO2CH2CH3, (Sp)-7) have been prepared by alkenylation of (Sp)-2-(diphenylphosphanyl)ferrocenecarboxaldehyde and tested as ligands for enantioselective palladium-catalysed allylic alkylation of 1,3-diphenyprop-2-en-1-yl acetate with dimethyl malonate. All phosphanylalkenes formed active catalysts. However, the induced enantioselectivity was only poor to moderate [12-43% ee after 20 h at room temperature], with the ee’s and configuration of the preferred product strongly depending on the ligand structure. The catalytic results have been related to solution properties (NMR, ESI MS) and the solid-state structural data (X-ray diffraction) of [Pd(η3-1,3-Ph2C3H3){(Sp)-22P}]ClO4 ((Sp)-12), which represent a model of the plausible reaction intermediate.  相似文献   

11.
Using 4-ethynylphenylferrocene (1) as the building block, a new series of rigid-rod alkynylferrocenyl precursors consisting of fluoren-9-one unit, 2-bromo-7-(4-ferrocenylphenylethynyl)fluoren-9-one (2a), 2,7-bis(4-ferrocenylphenylethynyl)fluoren-9-one (2b), 2-trimethylsilylethynyl-7-(4-ferrocenylphenylethynyl)fluoren-9-one (3) and 2-ethynyl-7-(4-ferrocenylphenylethynyl)fluoren-9-one (4) have been prepared in moderate to good yields. The acetylene complex 4 is a useful precursor for the synthesis of well-defined carbon-rich ferrocenyl heterometallic complexes, trans-[(η5-C5H5)Fe(η5-C5H4)C6H4CCRCCPt(PEt3)2Ph] (5), trans-[(η5-C5H5)Fe(η5-C5H4)C6H4CCRCCPt(PBu3)2CCRC≡CC6H45-C5H4)Fe(η5-C5H5)] (6), trans-[(η5-C5H5)Fe(η5-C5H4)C6H4CCRCCM(dppm)2Cl] (M=Ru (7), Os (8)) (R=fluoren-9-one-2,7-diyl). All new complexes have been characterized by FTIR, NMR and UV-Vis spectroscopies and fast atom bombardment mass spectrometry (FABMS). The molecular structures of 1, 2a, 4, 6 and 8 have been determined by single-crystal X-ray studies where an ironiron through-space distance of nanosized dimension (ca. 42 Å) is observed in the trimetallic molecular rod 6. The electronic absorption, luminescence and electrochemical properties of these carbon-rich molecules were investigated and the data were correlated with the theoretical results obtained by the method of density functional theory.  相似文献   

12.
13.
The half-sandwhich ruthenium chloro complexes bearing chelated diphosphazane ligands, [(η5-Cp)RuCl{κ2-P,P-(RO)2PN(Me)P(OR)2}] [R = C6H3Me2-2,6] (1) and [(η5-Cp)RuCl{κ2-P,P-X2PN(R)PYY′}] [R = Me, X = Y = Y′ = OC6H5 (2); R = CHMe2, X2 = C20H12O2, Y = Y′ = OC6H5 (3) or OC6H4tBu-4 (4)] have been prepared by the reaction of CpRu(PPh3)2Cl with (RO)2PN(Me)P(OR)2 [R = C6H3Me2-2,6 (L1)] or by the reaction of [CpRuCl2]n with X2PN(R)PYY′ in the presence of zinc dust. Among the four diastereomers (two enantiomeric pairs) possible for the “chiral at metal” complexes 3 and 4, only two diastereomers (one enantiomeric pair) are formed in these reactions. The complexes 1, 2, 4 and [(η5-Cp)RuCl{κ2-P,P-Ph2PN((S)-CHMePh)PPhY}] [Y = Ph (5) or N2C3HMe2-3,5 (SCSPRRu)-(6)] react with NaOMe to give the corresponding hydride complexes [(η5-Cp)RuH{κ2-P,P-(RO)2PN(Me)P(OR)2}] (7), [(η5-Cp)RuH{κ2-P,P′-X2PN(R)PY2}] [R = Me, X = Y = OC6H5 (8); R = CHMe2, X2 = C20H12O2, Y = OC6H4tBu-4 (9)] and [(η5-Cp)RuH{κ2-P,P-Ph2PN((S)-CHMePh)PPhY}][Y = Ph (10) or N2C3HMe2-3,5 (SCSPRRu)-(11a) and (SCSPSRu)-(11b)]. Only one enantiomeric pair of the hydride 9 is obtained from the chloro precursor 4 that bears sterically bulky substituents at the phosphorus centers. On the other hand, the optically pure trichiral complex 6 that bears sterically less bulky substituents at the phosphorus gives a mixture of two diastereomers (11a and 11b). Protonation of complex 7 using different acids (HX) gives a mixture of [(η5-Cp)Ru(η2-H2){κ2-P,P-(RO)2PN(Me)P(OR)2}]X (12a) and [(η5-Cp)Ru(H)22-P,P-(RO)2PN(Me)P(OR)2}]X (12b) of which 12a is the major product independent of the acid used; the dihydrogen nature of 12a is established by T1 measurements and also by synthesizing the deuteride analogue 7-D followed by protonation to obtain the D-H isotopomer. Preliminary investigations on asymmetric transfer hydrogenation of 2-acetonaphthone in the presence of a series of chiral diphosphazane ligands show that diphosphazanes in which the phosphorus centers are strong π-acceptor in character and bear sterically bulky substituents impart moderate levels of enantioselectivity. Attempts to identify the hydride intermediate involved in the asymmetric transfer hydrogenation by a model reaction suggests that a complex of the type, [Ru(H)(Cl){κ2-P,P-X2PN(R)PY2}(solvent)2] could be the active species in this transformation.  相似文献   

14.
New series of mono and binuclear arene ruthenium complexes [{(η6-arene)RuCl(L)}]+ and [{(η6-arene)RuCl}2(μ-L)2]2+ (arene=benzene, p-cymene or hexamethylbenzene), {L=pyridine-2-carbaldehyde azine (paa), p-phenylene-bis(picoline)-aldimine (pbp) and p-bi-phenylene-bis(picoline)-aldimine (bbp)} are reported. The complexes have been fully characterized and molecular structure of the representative mononuclear complex [(η6-C6Me6)RuCl(paa)]BF4 (1), binuclear complexes [{(η6-C10H14)RuCl}2(μ-paa)](BF4)2 (3) and [{(η6-C10H14)RuCl}2(μ-pbp)](BF4)2 (6) have been determined by single crystal X-ray diffraction analyses. Single crystal X-ray structure determination revealed that in the binuclear complexes the [(η6-C10H14)RuCl]+ units are trans disposed. Further, the crystal packing in the complexes 1, 3 and 6 is stabilized by C-H?X type (X=Cl, F) inter, intramolecular hydrogen bonding and π-π stacking (3). To explore the ambiguous nature of the bonding between pyridine-2-carbaldehyde azine (paa) with ruthenium containing units [(η6-arene)RuCl]+, DFT/B3LYP calculations have been performed on the complexes [(η6-arene)RuCl(paa)]+ (arene=C6H6, I; C6Me6, II; C10H14, III).  相似文献   

15.
A series of novel amphiphilic ferrocenylimines and their cyclopalladated complexes of general formula [Fe(η5-C5H5)(η5-C5H4CR1NR2)] (R1=H, R2=C12H25-n4a, R1=H, R2=C16H33-n4b, R1=CH3, R2=C12H25-n4c, R1=CH3, R2=C16H33-n4d), [PdCl{[(η5-C5H5)]Fe[(η5-C5H3)CR1NR2]}]2 (5a-d), [PdCl{[(η5-C5H5)]Fe[(η5-C5H3)-CR1NR2]}(PPh3)] (6a-d), were prepared and characterized by 1H NMR, 13C NMR, 31P NMR, IR, HRMS, and elemental analysis. The crystal structures of 5c,d were determined by X-ray crystallography. These amphiphilic cyclopalladated complexes are thermally stable and insensitive to oxygen and moisture. The redox properties of 4a-d, 5a-d, 6a-d were also investigated using cyclic voltammetric technique. Compounds 5a-d, 6a-d displayed good activity in the Heck reaction of a variety of aryl halides with ethyl acrylate or styrene and the Suzuki-Miyaura cross-coupling reaction of aryl bromides with phenylboronic acid in bulk solution. They are also suitable for formation of Langmuir-Blodgett (LB) films.  相似文献   

16.
While photochemical reaction of C60 with an equimolar amount of Mo(CO)46-Ph2PC6H5)2Cr (1) in toluene at room temperature produced bimetallic Mo/Cr fullerene complex fac/mer-(η2-C60)Mo(CO)3[(η6-Ph2PC6H5)2Cr] (2) in 87% yield, the thermal reaction of an equimolar mixture of C60, M(dba)2 (M = Pd, Pt; dba = dibenzylideneacetone) and (η6-Ph2PC6H5)2Cr (3) in toluene at room temperature afforded bimetallic M/Cr fullerene complexes (η2-C60)M[(η6-Ph2PC6H5)2Cr] (4, M = Pd; 5, M = Pt) in 88% and 92% yields, respectively. Products 2, 4 and 5 are the first transition-metal fullerene complexes containing bis(η6-benzene)chromium moieties. While 2, 4 and 5 were characterized by elemental analysis and spectroscopy, the crystal molecular structures of 4 along with the starting materials 1 and 3 have been determined by X-ray diffraction techniques.  相似文献   

17.
Complexes [Pd(η1, η2-5-OMe-C8H12)(N,O)]BF4 (N,O=2,6-(i-Pr)2(C6H3)NC(Ph)-C(Ph)O, 1; 2,6-(i-Pr)2(C6H3)NC(Me)-C(Ph)O, 2; 2-benzoylpyridine, 3) were synthesized by the reactions of [Pd(η12-5-OMe-C8H12)Cl]2 with the suitable N,O-ligand. They were tested as catalysts for olefin or alkyne polymerizations. During such reactions 1-3 quantitatively transformed into their η12-1-OMe-C8H12 isomers (1a-3a). The same isomerization occurred in methylene chloride, even in the absence of olefins or alkynes, with a much slower rate. All complexes were fully characterized in solution by multinuclear and multidimensional low temperature NMR spectroscopy. The solid state structures of complexes 1 and 1a were investigated by X-ray single crystal studies. 19F, 1H-HOESY NMR experiments carried out in methylene chloride-d2 at 217 K indicated that the anion prefers to locate on the side of N,O-ligand shifted toward the O-arm in 1-1a and 2-2a while it approaches the N-arm in 3 and 3a compounds.  相似文献   

18.
The dimeric starting material [Ru(η6-p-cymene)(μ-Cl)Cl]2 reacts with the phosphino-amides o-Ph2P–C6H4CO–NH–R [R = iPr (a), Ph (b), 4-MeC6H4 (c), 4-FC6H4 (d)] to give the mononuclear compounds 1ad [RuCl(η6-p-cymene)(o-Ph2P–C6H4–CO–NH–R)]Cl. The subsequent reaction of these complexes with KPF6 produced the cationic species 2ad [RuCl(η6-p-cymene)(o-Ph2P–C6H4–CO–NH–R)][PF6] in which phosphino-amides also act as rigid P,O-chelating ligands. The molecular structures of 2bd were determined crystallographically. Amide deprotonation is achieved when complexes 2ad were made react with 1 M aqueous solution of KOH, affording the corresponding neutral species 3ad [RuCl(η6-p-cymene)(o-Ph2P–C6H4–CO–N–R)] in which a P,N-coordination mode is suggested.  相似文献   

19.
Reactions between [Fe(η-C5H5)(MeCO)(CO)(L)], L = PPh3 (1), PMe3 (2), PPhMe2 (3), PCy3 (4), CO (5), and B(C6F5)3 give new complexes [Fe(η-C5H5){MeCOB(C6F5)3}(CO)(L)] L = PPh3 (7), PMe3 (8), PPhMe2 (9), PCy3 (10), CO (11), where B(C6F5)3 coordinates selectively to the O-acyl groups. Hydrolysis of 7 gives [Fe(η-C5H5){HOB(C6F5)3}(CO)(PPh3)] (6). The X-ray structures of 6, 8 and 11 have been determined. Calculations, using density functional theory, demonstrate that the charge transfer to the acyl group on Lewis acid coordination is more significant in the σ than the π system. Both effects lead to a lengthening of the acyl C-O bond thus π populations cannot be inferred from the distance changes.  相似文献   

20.
Reactions of the trans-PdCl2(PPh3)2 precursor with furan-2-carbaldehyde thiosemicarbazone (Hftsc) and thiophene-2-carbaldehyde thiosemicarbazone (Httsc), in 1:1 molar ratios in the presence of Et3N base, removed one Cl and one PPh3 group from the PdII center, and yielded the complexes [Pd(η2-N3,S-ftsc)(PPh3)Cl] (1) and [Pd(η2-N3,S-ttsc)(PPh3)Cl] (2), respectively. However, when a 1:2 molar ratio (M:L) was used, both Cl and PPh3 ligands were removed, yielding the complexes trans-[Pd(η2-N3,S-ftsc)2] (3) and trans-[Pd(η2-N3,S-ttsc)2] (4). Complexes 14 have been characterized with the help of analytical data, spectroscopic techniques (IR, 1H and 31P NMR) and single crystal X-ray crystallography. The thiosemicarbazone ligands behave as uninegative N3,S-chelating ligands in complexes 14. In contrast, pyrrole-2-carbaldehyde thiosemicarbazone (H2ptsc) and salicylaldehyde thiosemicarbazone (H2stsc) invariably formed the complexes [Pd(η3-N4,N3,S-ptsc)(PPh3)] (5) and [Pd(η3–O, N3,S-stsc)(PPh3)] (6), respectively, and the ligands acted as binegative tridentate donors (N4, N3, S, 5; O, N3, S, 6).  相似文献   

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