69451 Weinheim, Germany - Wiley-VCH
Supporting Information Wiley-VCH 200769451 Weinheim, Germany
Controlled rotary motion in a monolayer of molecular motors†‡‡†Michael M. Pollard , Monika Lubomska , Petra Rudolf* and Ben L. Feringa*†Contribution from the Department of Organic and Molecular Inorganic Chemistry, Stratingh Institute,University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands; and ‡Materials ScienceCentre, Rijksuniversiteit Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands.ContentsCONTROLLED ROTARY MOTION IN A MONOLAYER OF MOLECULAR MOTORS . 1GENERAL REMARKS. 2GENERAL REMARKS FOR SYNTHETIC PROCEDURES:. 2SPECTROSCOPY (NMR, UV, CD). . 2SYNTHESIS OF COMPOUNDS AND INTERMEDIATES . cenone oanthracenone S3.4Episulfide S6 .4Motor diester 1 .5Unstable-1 .5Motor diacid S7.6(R)-(M)-S7 .7Motor diacid chloride 3 .7(R)-(M)-3 .7Diester S9 .7Thioketone diester S10.8Episulfides cis-S11 and trans-S11 .8Overcrowded alkenes cis-2 and trans-2.9Irradiation experiment to generate unstable isomers: .9MATERIALS AND METHODS (SURFACES). 11EXPERIMENTAL PROCEDURES FOR SURFACE MODIFICATION . 11AMINOPROPYLTRIETHOXYSILANE (APTES) MONOLAYER ON QUARTZ . 11Stable-(R)-(M)-4 (Motor monolayer on quartz plates) .11CIRCULAR DICHROISM (CD) SPECTROSCOPY . 11Cleaning of Silicon substrates .15Silicon oxide bound motor on silicon for XPS analysis 5 .15XPS MEASUREMENTS . 15XPS of APTES SAM on silicon wafers . 16XPS OF 5 . 17XPS summary. 19NMR SPECTRA. 221
General remarksGeneral remarks for synthetic procedures:Reagents were purchased from Aldrich, Acros, Strem, Merck or Fluka and were used as providedunless otherwise stated. All solvents were reagent grade and were dried and distilled before useaccording to standard procedures. All reactions were performed in oven- or flame-dried roundbottomed or modified Schlenk (Kjeldahl shape) flasks fitted with rubber septa under a positive pressureof nitrogen, unless otherwise noted. Air- and moisture-sensitive liquids and solutions were transferredvia syringe or stainless steel cannula. Organic solutions were concentrated by rotary evaporation 30–40 C. Flash column chromatography was performed as described by Still et al. (Still, W. C.; Kahn, M.;Mitra, A. J. Org. Chem. 1978, 43, 2923-2925.) Chromatography: silica gel, Merck type 9385 230-400mesh.TLC: silica gel 60, Merck, 0.25 mm, impregnated with a fluorescent indicator (254 nm). TLC plateswere visualized by exposure to ultraviolet light (UV) and/or exposure to ceric ammonium molybdatesolution (CAM) or an acidic solution of p-anisaldehyde (anisaldehyde) followed by brief heating with aheating gun.Mass spectra (HRMS) were recorded on an AEI MS-902. Melting points were recorded on a BüchiB-545 melting point apparatus and are uncorrected. 1H and 13C NMR spectra were recorded on a VarianVXR-300 a Varian Mercury Plus, or a Varian Inova 500 operating at 299.97, 399.93, and 499.98 MHz,respectively, for the 1H nucleus, and at 75.43, 100.57 and 124.98 MHz for the 13C nucleus.Irradiation experiments were performed using a Spectroline model ENB-280C/FE lamp at λ 365nm, 30 nm. NMR samples were placed 2-3 cm from the lamp.Spectroscopy (NMR, UV, CD).Chemical shifts for protons are reported in parts per million scale (δ scale) downfield fromtetramethylsilane and are referenced to residual protium in the NMR solvents CHCl3: δ 7.26, C6D5H: δ7.15, CD2HCOD: δ 3.31, CD2HCN δ 1.93). Chemical shifts for carbon are reported in parts per million(δ scale) downfield from tetramethylsilane and are referenced to the carbon resonances of the solvent(CDCl3: δ 77.0, C6D6: δ 128.0, D3COD: δ 44.9). Data are represented as follows: chemical shift,multiplicity (s singlet, d doublet, t triplet, q quartet, m multiplet, br broad), integration,coupling constant in Hz, and assignment. Solution CD spectra were recorded on a JASCO J-715spectropolarimeter using UVASOL grade hexane or heptane in a 1.0 cm quartz cell at ambienttemperature unless otherwise specified.UV spectra were obtained using Hewlet-Packard HP 8543 FT spectrophotometer in a 1 cm quartzcuvette.Solution CD spectra were recorded using a Jasco J715 spectropolarimeter and a JASCO PFD350S/350L Peltier-type FDCD attachment with a temperature control with a 1.0 cm cell with thefollowing conditions: speed 100 nm/min, response time, 1 s; bandwidth 1 nm (solution) or 10 nm(surface), noise reduction was carried out on the spectrum of stable-(R)-(M)-4.2
Synthesis of compounds and intermediatesOOcat. NaOMeMeOH, THFSBenzene, , P2S5Methyl AcrylateS1MeO2CCO2MeMeO2CCO2MeS3S2SSSS3Ag2O, 0 oCH2NKOH, H2O, THF95% MeO2CCO2MeHO2C1(Enantiomers resolved here)CO2HClOCS7COCl3Figure S1: Preparation of parent compound 1 and di-acid chloride 3.OOcat. NaOMeMeOH, THF OOBenzene, , P2S5SOMethyl AcrylateS8MeO2CCO2MeMeO2CCO2MeS10S9SSSS10Ag2O, 0 oCH2NKOH, CH2Cl2NS4OSNNMeO2CS5CO2Metrans-S11 cis-S11SSCu,XyleneOO re S2: Synthesis of cis-2 and trans-2.3
OOcat. NaOMeMeOH, THFMethyl AcrylateOOO cenone S2The diester was prepared in 87% yield according to the procedure of Rickborn.1SOP2S5Toluenereflux, 3hOOOOO OO thracenone S3Ketone S2 (1.10 g, 3.00 mmol) and P2S5 (1.33 g, 3.00 mmol) were suspended in toluene (10 mL) andheated at 90 C for 3 h. TLC of the reaction mixture showed no evidence of starting material. Themixture was allowed to cool to rt, and then filtered through a plug of silica (1 cm thick, 3 cm diameter).The silica was washed with 10% CH2Cl2 in toluene until no green coloured material eluted further.Then the combined reaction mixture and washings were concentrated in vacuo to give a green residuewhich solidified to a waxy solid upon standing in the fridge, which was judged 90 % pure by 1H NMR,and is suitable for use in further transformations (recommended). For analytical purposes, this residuewas purified by flash chromatography (Hex/EtOAc, 3/1-2/1) to give 710 mg (1.95 mmol, 65%) of agreen oil which solidified to a wax upon standing. This material should be stored in the fridge underinert atmosphere to minimize degradation. NB: Pure material left at 40 C under reduced pressuredegraded to a mixture of starting material and to a complex mixture of degradation products. IR (cast,CH2Cl2) 2950, 1735, 1197; 1H NMR (300 MHz, CDCl3) 1.51-1.61 (AA’BB’, 4H), 2.50-2.60 (AA’BB’,4H), 3.39 (s, 6H), 7.33 (t, 2H, J 7.5 Hz), 7.53 (AB d, 2H, Japparent 8.1 Hz), 7.63 (ABX t, 2H, Japparent 8.1 Hz), 8.67 (d, 2H, J 8.1 Hz); 13C NMR (APT, 75 MHz, CDCl3) 218.5, 173.1, 139.3, 139.0, 133.8,131.2, 127.5, 125.5, 51.4, 45.7, 39.8, 29.0; HRMS (EI) calcd C22H22O4S 382.1239, found 382.1256.S1) MgSO4, Ag2O,DCM, KOH in MeOH0CSNNH2S2) ThioketoneOOO OEpisulfide S6Ag2O (500 mg) was added to a stirred suspension of hydrazone S42 (330 mg, 1.36 mmol) and MgSO4(500 mg) in CH2Cl2 (5 mL) at 0 C. After stirring for 10 min, the solution turned dark red (if thesolution did not turn red within 1 min of addition, 5 drops of a saturated solution of KOH in dry MeOHwere added). Subsequent to the colour change, the suspension was stirred an additional 30 min. Themixture was filtered at 0 C, and the solid rinsed with an additional 4 mL of CH2Cl2. A solution ofthioketone (530 mg, 1.40 mmol) in CH2Cl2 was added to the stirred red solution of diazo compound.Nitrogen gas evolution was observed. The mixture was stirred for 4 h, then reduced in vacuo. This4
residue was purified by flash chromatography (4/1 Hex.EtOAc to 3/1) to give the episulfide as acolourless solid (662 mg, 82%). Yields range reproducibly between 62-82%. 1H NMR (CDCl3, 300MHz) δ 1.18 (d, 3H, J 6.6 Hz), 1.30-1.41 (m, 2H), 2.20-2.30 (m, 2H), 2.35-2.64 (m, 4H), 2.64-2.80(m, 2H), 3.10-3.20 (m, 1H), 3.45 (s, 3H), 3.71 (s, 3H), 6.14 (t, 1H, J 7.5 Hz), 6.62 (d, 1H, 8.4 Hz),6.84 (d, 1H, J 8.4 Hz), 6.87 (t, 1H, J 6.6 Hz), 7.18 (d, 1H, J 8.1 Hz), 7.30-7.45 (m, 4H), 7.45-7.60(m, 2H), 7.69 (d, 1H, J 8.1 Hz), 8.10 (d, 1H, J 7.5 Hz), 8.90 (d, 2H, J 8.7 Hz); 13C NMR (CDCl3,100 MHz, APT) 20.3 (CH3), 29.2 (CH2), 31.4 (CH2), 33.9 (CH2), 37.7 (CH2), 38.4 (CH), 39.5 (CH2),44.8 (CH2), 51.2 (CH3), 51.6 (CH3), 57.5 (C), 63.9 (C), 122.5 (CH), 124.1 (CH), 124.3 (CH), 125.0(CH), 125.4 (CH), 126.6 (CH), 126.9 (CH), 127.1 (CH), 127.9 (CH), 128.0 (C), 128.3 (CH), 129.1(CH), 130.1 (C), 131.9 (C), 132.9 (C), 132.7 (C), 134.1 (C), 135.6 (C), 137.0 (C), 140.1 (C), 142.5 (C),173.8 (C), 174.0 (C). HRMS (EI) calcd C36H34O4S2 594.1898, found 594.1909.SSp-xylene, refluxStriphenylphosphineOOOOO OO OMotor diester 1A solution of episulfide (660 mg, 1.08 mmol) and Cu bronze (1.00 g) was heated at reflux in p-xyleneunder inert atmosphere for 18h. The solvent was distilled in vacuo, and the mixture purified by flashchromatography (4/1 3/1) to give 625 mg (94%) of alkene. mp 164.3-165.1 C, (1H NMR, 400 MHz,CDCl3) δ 0.79 (d, 3H, J 6.4 Hz), 1.95-2.15 (m, 2H), 2.38 (dd, 1H, J 16.8, 12.4 Hz), 2.44-2.62 (m,2H), 2.62 (m, 2H), 2.78-2.89 (m, 1H), 3.00 (dd, 1H, J 2.6, 12.0 Hz), 3.62-3.7 (m, 1H), 3.65 (s, 6H),4.30-4.40 (m, 1H), 6.22 (AB, 1H, Japparent 7.2 Hz), 6.29 (ABM d, 1H, Japparent 7.0 Hz), 6.84 (t, 1H, J 7.8 Hz), 6.92 (t, 1H, J 7.2 Hz), 7.16 (t, 1H, J 7.2 Hz), 7.18-7.26 (m, 2H), 7.36 (t, 1H, J 7.2 Hz),7.40 (t, 1H, J 7.4 Hz), 7.50 (dd, 1H, J 8.3, 1.0 Hz), 7.55 (d, 1H, J 7.2 Hz), 7.65 (d, 1H, J 8.4Hz), 7.68 (d, 1H, J 8.8 Hz), 7.76 (d, H, J 7.2 Hz); (13C NMR, 100 MHz, CDCl3) 20.7, 28.3, 29.3,30.2, 34.7, 37.2, 37.9, 46.4, 31.6, 51.7, 124.3, 124.6, 124.8, 125.1, 125.4, 125.6, 126.0, 126.8 (2 signalsoverlapping), 127.3, 127.4, 127.8, 128.21, 128.25, 130.6, 131.2, 131.9, 134.5, 135.2, 136.3, 137.0,137.7, 142.6, 173.6, 174.2. HRMS (EI) calcd for C36H34O4S, found 562.2178, found 562.2163. Theenantiomers of 1 were resolved using a Chiralcel OD column eluting with 4% iPrOH in Heptane at 1mL/min detecting at 280 nm: retentiontimes for enantiomers A: 8.11 min, and B; 9.68 2CCO2Meunstable-(R)-(P)-1Unstable-1A solution of 2 mg of stable-1 in nitrogen purged C6D6 (0.7 mL) was irradiated at 365 nm 1 cm from thelamp for 2 min time intervals and analysed by 1H NMR until a PSS was reached (approx 20 min). A4.5/1 mixture of unstable-1/stable-1 was obtained. Data for unstable-1: (1H NMR, 400 MHz, C6D6) δ0.89 (d, 3H, J 7.5 Hz), 1.85-2.05 (m, 2H), 2.30-2.34 (m, 1H), 2.40-2.55 (m, 3H), 2.55-2.65 (m, 1H),2.65-2.80 (m, 2H), 2.89 (t, 1H, J 10.3 Hz), 3.05 (t, 1H, J 9.0 Hz), 3.31 (s, 3H), 3.34 (s, 3H), 6.13 (t,1H, J 7.3 Hz), 6.39 (d, 1H, J 7.0 Hz), 6.57 (t, 1H, J 7.8 Hz), 7.01 (d, 1H, J 8.5 Hz), 7.03-7.155
(m, 2H), 7.35 (d, 1H, J 8.0 Hz), 7.44 (d, 1H, J 8.0 Hz), 7.49 (d, 1H, J 7.0 Hz), 7.55 (d, 1H, J 9.0Hz), 7.57 (d, 1H, J 9.5 Hz).Figure S3: UV spectra of stable-1 (red dotted) and unstable-1 (blue solid) in hexane.1.00.80.60.4 th (nm)Figure S4: CD spectrum of stable-(R)-(M)-1 (black) and unstable (R)-(P)-1 (red) in hexane.SS2N LiOHEtOHTHF4h95%OOO OOOOH OHMotor diacid S7A solution of LiOH (96 mg, 4 mmol) in water and EtOH (1:1, 4 mL total) was added to a solution of 1(300 mg, 0.51 mmol) in THF (2 mL). This mixture was stirred under inert atmosphere for 4 h, thenacidified to pH 2 with dilute aqueous HCl and extracted with EtOAc (3 x 6 mL). The combined organic6
extracts were washed with water (2 x 5 mL) brine (3 mL), dried (Na2SO4) and reduced in vacuo to give265 mg (0.47 mmol) of a white solid. TLC: Rf 0.21 in Hex/EtOAc 1/1, 1% AcOH. mp 273 C(dec.),1H NMR (300 MHz, CD3OD) δ 0.71 (d, 3H, J 6.6 Hz), 1.72-2.10 (m, 2H), 2.20-2.80 (m, 5H), 2.803.00 (m, 2H), 3.68 (dd, 1H, J 9.3, 11.7 Hz), 4.25-4.40 (m, 1H), 6.15 (dd, 1H, J 1.1, 7.5 Hz), 6.23 (t,1H, J 7.1 Hz), 6.82 (dt, 1H, J 1.4, 8.4 Hz), 6.95 (d, 1H, J 7.5 Hz), 7.12 (t, 1H, J 7.2 Hz), 7.207.32 (m, 2H), 7.33-7.43 (m, 2H), 7.46 (d, 1H, J 8.4 Hz), 7.51-7.72 (m, 3H), 7.73-7.78 (m, 2H); 13CNMR (APT, 100 MHz, CH3OD) δ 20.9 (CH3), 29.3 (CH2), 30.6 (CH2), 31.2 (CH2), 36.2 (CH), 38.1(CH2), 39.4 (CH2), 48.0 (C), 125.7 (CH), 125.8 (2 x CH), 126.5 (CH), 126.78 (CH), 126.81 (CH), 127.1(2 x CH), 127.8 (CH), 128.5 (CH), 128.6 (CH), 128.96 (CH), 129.03 (CH), 129.4 (CH), 132.1 (C),132.8 (C), 133.6 (C), 136.0 (C), 136.9 (C), 137.7 (C), 138.4 (C), 139.5 (C), 139.8 (C), 144.0 (C), 177.0(C), 178.4 (C) 2 aromatic carbons overlapping., HRMS calcd C34H30O4S 534.1844, found 534.1865.(R)-(M)-S7The procedure used was identical to the racemate, except scaled to use 15 mg of (R)-(M)-1.SSC2O2Cl2HO2CCO2HClOCS7COCl3Motor diacid chloride 3SOCl2 (200uL) was added to a stirred solution of S7 in CH2Cl2 (2 mL). After 3 h, the solvent wasremoved in vacuo, the mixture redissolved in CH2Cl2 and concentrated in vacuo (3x), and left underunder reduced pressure for 3 h. 1H NMR (300 MHz, CDCl3) δ 0.79 (d, 3H, J 6.8 Hz), 2.40-2.90 (m,6H), 3.07 (dd, 1H, J 3.0, 7.8 Hz), 3.00-3.22 (m, 2H), 3.63 (dd, 1H, J 9.3, 11.7 Hz), 4.25-4.40 (m,1H), 6.15 (dd, 1H, J 1.1, 7.5 Hz), 6.23 (t, 1H, J 7.1 Hz), 6.82 (dt, 1H, J 1.4, 8.4 Hz), 6.95 (d, 1H, J 7.5 Hz), 7.12 (t, 1H, J 7.2 Hz), 7.20-7.32 (m, 2H), 7.33-7.43 (m, 2H), 7.46 (d, 1H, J 8.4 Hz), 7.517.72 (m, 3H), 7.73-7.78 (m, 2H).(R)-(M)-3The procedure used was identical to the racemate, except scaled to use 11 mg of (R)-(M)-S7.OOOMethyl acrylateMeOHcat MeONaOMeO2CCO2MeDiester S9A solution of 2-methoxyanthrone3 (2.24 g, 10.0 mmol) and methyl acrylate (1.89 g, 22.0 mmol) inMeOH (30 mL) was added dropwise to a vigorously stirred solution of MeONa (108 mg, 2.00 mmol) inMeOH (100 mL) under inert atmosphere. The solution was stirred for 5 h, acidified by the addition of2% aqueous HCl (100 mL) and brine (20 mL), extracted with EtOAc (2 x 200 mL), the organic layerwashed sat’d aqueous NaHCO3 (1 x 100 mL) with brine (20 mL) and dried (Na2SO4). Concentration invacuo gave a orange residue, which was purified by flash chromatography to give 3.41 g (86 %) of ayellow solid. mp 109.1-109.9 C; (1H NMR, 400 MHz, CDCl3) δ 1.52-1.58 (m, 4H), 2.50-2.60 (m,4H), 3.42 (s, 6H), 3.90 (s, 3H), 7.24 (dd, 1H, J 8.8, 2.8 Hz), 7.45 (ddd, 1H, J 1.2, 7.4, 8.0 Hz), 7.527
(d, 1H, J 8.8 Hz), 7.61 (d, 1H, J 7.6 Hz), 7.66 (dt, 1H, J 1.2, 8.2 Hz), 7.81 (d, 1H, J 2.8 Hz),8.36 (dd, 1H, J 1.6, 8.0 Hz); 13C NMR (100 MHz, CDCl3) 29.1, 39.6, 44.5, 51.5, 55.6, 108.9, 123.2,125.9, 127.4, 127.5, 127.8, 132.6, 133.8, 134.3, 137.3, 145.1, 158.7, 173.2, 183.0. HRMS (EI) calcd forC23H24O6 396.1577 found 396.1573.OSOOMeO2CCO2MeMeO2CCO2MeThioketone diester S10A suspension of ketone (396 mg, 1.00 mmol) and P4S10 (444 mg, 1.00 mmol) was heated at 65 C for 12h followed by cooling to rt. The mixture was then filtered through silica gel, and rinsed with 30%CH2Cl2 in toluene until the washings were colourless. The filtrate was concentrated in vacuo to 4 mLand purified by column chromatography (Heptane/EtOAc, 4/1) to give the title compound as a greensolid (302 mg 73%). mp 113.5-114.5 C, 1H NMR (C6D6, 300 MHz) δ 1.50-1.65 (ABXY, 4H), 2.402.52 (ABXY, 4H), 3.08 (s, 3H), 3.39 (s, 3H), 6.95-7.25 (m, 5H), 8.47 (d, 1H, J 3.0 Hz), 8.95 (d, 1H, J 8.1 Hz); 13C NMR (CDCl3, 75 MHz) δ 29.0, 39.6, 45.3, 51.4, 55.4, 112.7, 122.6, 125.6, 127.1, 127.4,131.4, 131.8, 133.6, 139.3, 140.4, 158.5, 173.2, 217.9; HRMS (EI) calcd for C23H24O5S 412.1244,found 412.1350.SSNNSSOOMeO2CSSO CO2MeMeO2CCO2MeMeO2CCO2MeRacemicEpisulfides cis-S11 and trans-S11Silver oxide (454 mg, 2.00 mmol) was added to a solution of recrystallized hydrazone S42 (242 mg,1.00 mmol) and Na2SO4 (282 mg, 2.00 mmol) in CH2Cl2 (5 mL) at 0 C. If the solution did not turn redspontaneously, 3 drops of a saturated solution of KOH in MeOH was added. After the solution turnedslightly red, the mixture was stirred an additional 15 min, then quickly filtered over a cotton plug into asolution of thioketone (412 mg, 1.00 mmol) in CH2Cl2 (4 mL). N2 evolution was observed. Thismixture was stirred for 4 h, concentrated in vacuo, and purified by flash chromatography (SiO2;Heptane/EtOAc, 4/1) to give 260 mg (44% yield) of the product as a 1:1.2 mixture of cis/trans isomers.An analytical sample was separated by flash chromatography (SiO2; Heptane/EtOAc, 4/1) forcharacterization.cis-S11: 1H NMR (400 MHz, CDCl3) δ 1.14 (d, 2H, J 7.6 Hz), 1.34 (t, 2H, J 8.1 Hz), 2.20-2.30 (m,2H), 2.20-2.45 (m, 2H), 2.45-2.85 (m, 5H), 2.58 (s, 3H), 3.12-3.22 (m, 1H), 3.45 (s, 3H), 3.76 (s, 3H),6.31 (d, 1H, J 2.8 Hz), 6.47 (dd, 1H, J 8.8, 3.2 Hz), 6.92 (d, 1H, J 8.4 Hz), 7.07 (d, 1H, J 8.8Hz), 7.32 (t, 1H, J 7.8 Hz), 7.35 – 7.45 (m, 3H), 7.50-7.58 (m, 2H), 7.71 (d, 1H, J 8.4 Hz), 8.09 (d,1H, J 8.0Hz), 8.94 (d, 1H, J 8.0 Hz); 13C NMR (100 MHz, CDCl3) δ 20.4, 29.2, 31.5, 33.9, 37.9,38.6, 39.4, 44.3, 51.3, 51.60, 53.5, 57.7, 63.9, 111.5, 111.6, 115.9, 122.6, 124.4, 125.4, 125.6, 126.09,126.10, 126.7, 127.3, 128.0, 128.2, 128.6, 130.2, 132.1, 132.4, 134.0, 134.4, 135.5, 137.3, 143.0, 156.1,173.9, 174.2.trans-S11: 1H NMR (500 MHz, CDCl3) δ 1.19 (d, 2H, J 6.5 Hz), 1.30-1.45 (m, 2H), 2.26 (dd, 2H, J 12, 4.5 Hz), 2.30-2.45 (m, 3H), 2.45-2.65 (m, 2H), 2.65-2.71 (m, 2H), 3.15-3.25 (m, 1H), 3.45 (s, 3H),3.71 (s, 3H), 3.89 (s, 3H), 6.12 (dd, 1H, J 7.8, 9.2 Hz), 6.60 (dd, 1H, J 6.5, 1.3 Hz), 6.82 (d, 1H, J 8
8.0 Hz), 6.86 (d, 1H, J 8.8 Hz), 6.98 (dd, 1H, J 9.0, 3.0 Hz), 7.15 (dd, 1H, J 7.5, 1.0 Hz), 7.34 (d,1H, J 8.5 Hz), 7.40 (dt, 1H, J 1.0, 6.5 Hz), 7.47 (d, 1H, 9.0 Hz), 7.54 (dt, 1H, 1.3, J 7.8 Hz), 7.65(d, 1H, J 3.0 Hz), 7.67 (d, 1H, J 8.5 Hz), 8.89 (d, 1H, J 8.5 Hz); 13C NMR (100 MHz, CDCl3) δ20.3, 29.3, 31.5, 34.0, 37.5, 38.4, 39.7, 44.3, 51.4, 51.7, 55.3, 57.7, 63.9, 113.7, 115.5, 122.6, 124.1,124.3, 125.0, 125.5 (2 overlapped C), 126.9, 127.2, 127.7, 128.1, 128.3, 129.1, 131.9, 132.6, 134.7,135.6, 135.8, 137.1, 140.5, 156.9, 174.0, 174.2.SSOSCu,XyleneSOO MeO2CCO2Metrans-S11 s-2Overcrowded alkenes cis-2 and trans-2A solution of a mixture of episulfides cis-S11 and trans-S11 (200 mg, 0.33 mmol) and finely powderedCu (500 mg) was heated at reflux in p-xylene under inert atmosphere for 1 d. The solvent was distilledin vacuo, and the mixture purified by flash chromatography to give 180 mg of alkene (97%) as amixture of stable-cis-2 and stable-trans-2. Rf 0.24 (trans) and 0.29 (cis); 3/1 Hex/EtOAc (spots areblue fluorescent, and move slightly slower than the episulfide).stable cis-2: 1H NMR (400 MHz, CDCl3) δ 0.78 (d, 2H, J 7.2 Hz), 1.90-2.10 (m, 2H), 2.23-2.40 (m,1H), 2.40-2.70 (m, 4H), 2.70-2.82 (m, 1H), 2.86 (s, 3H), 2.95 (dd, 1H, J 11.6, 2.8 Hz), 3.60-3.70(unresolved due to overlap, 1H), 3.64 (s, 3H), 3.65 (s, 3H), 4.32-4.41 (m, 1H), 5.85 (d, 1H, J 3.2 Hz),6.38 (dd, 1H, J 8.8, 3.2 Hz), 6.97 (t, 1H, J 7.6 Hz), 7.06 (d, 1H, J 8.8 Hz), 7.18 (t, 1H, 7.4 Hz),7.25-7.40 (m, 3H), 7.45-7.55 (m, 2H), 7.60-7.68 (m, 2H), 7.72 (dd, 1H, J 2.0, 7.2 Hz); 13C NMR(100MHz, CDCl3) δ 20.7, 29.4, 30.3, 34.9, 37.2, 37.7, 45.9, 51.6, 51.7, 54.3, 111.7, 114.1, 124.3, 124.9,125.0, 125.5, 125.8, 126.6, 127.0, 127.3, 127.8, 128.2, 130.2, 130.9, 131.7, 131.9, 134.7, 135.2, 136.4,137.0, 138.9, 143.0, 156.6, 173.7, 174.2. (one carbon overlapping) HRMS calcd for C37H36O5S592.2283, found 592.2266.stable trans-2: 1H NMR (400 MHz, CDCl3) δ 0.79 (d, 2H, J 6.8 Hz), 1.80-2.15 (m, 2H), 2.23-2.40 (m,1H), 2.40-2.58 (m, 2H), 2.58-2.70 (m, 2H), 2.70-2.82 (m, 1H), 3.00 (dd, 1H, J 12.0, 3.6 Hz), 3.603.70 (unresolved due to overlap, 1H), 3.65 (s, 6H), 3.90 (s, 3H), 4.32-4.41 (m, 1H), 6.20 (AB, 1H,Japparent 8.4 Hz), 6.27 (ABM, 1H, Japparent 7.2 Hz), 6.82 (t, 1H, J 7.6 Hz), 6.85- 6.96 (m, 2H), 7.117.23 (m, 3H), 7.28 (d, 1H, J 2.8 Hz), 7.42 (d, 1H, J 8.8 Hz), 7.48 (d, 1H, J 8.4 Hz), 7.64 (d, 1H, J 8.0 Hz), 7.67 (d, 1H, J 7.6 Hz); 13C NMR (100 MHz, CDCl3) δ 20.7, 29.4, 30.3, 34.9, 37.2, 37.7,45.9, 51.6, 51.7, 54.3, 111.7, 114.1, 124.3, 124.9, 125.0, 125.5, 125.8, 126.6, 127.0, 127.3, 127.8, 128.2,130.2, 130.9, 131.7, 131.9, 134.7, 135.2, 136.4, 137.0, 138.9, 143.0, 156.6, 173.7, 174.2. HRMS calcdfor C37H36O5S 592.2283, found 592.2261.Irradiation experiment to generate unstable isomers:2 mg of stable-cis-2 was dissolved in CD3CN (this solvent was used to resolve signals originating fromall 4 isomers). This sample was placed in an NMR tube and irradiated with 365 nm light at a distance of2-3 cm from the centre of the lamp, under which conditions no heating of the sample occurred.stable-cis-2: 1H NMR (500 MHz, CD3CN) δ 0.70 (d, 3H, J 7.0 Hz), 1.77-2.00 (m, 2H), 2.29 (dt, 1H, J 5.0, 13.0 Hz), 2.37 (dt, 1H, J 3.8, 15.8 Hz), 2.44 (dt, 1H, J 3.5, 13.0 Hz), 2.50-2.65 (m, 2H), 2.702.80 (m, 1H), 2.87 (s, 3H), 2.95 (d, 1H, J 11.5 Hz), 3.56 (s, 3H), 3.58 (s, 3H), 3.68 (t, 1H, J 10.5Hz), 4.25-4.35 (m, 1H), 5.79 (d, 1H, J 2.0 Hz), 6.38 (dd, 1H, J 8.5, 3.0 Hz), 6.07 (t, 1H, J 7.5 Hz),7.16 (d, 1H, J 9.0 Hz), 7.23 (t, 1H, 7.5 Hz), 7.32 (d, 1H, J 8.5 Hz), 7.35-7.47 (m, 2H), 7.45 (d, 1H, J 8.0 Hz), 7.57 (d, 1H, J 8.5 Hz); 7.63-7.73 (m, 3H).9
unstable-cis-2: 1H NMR (400 MHz, CDCl3) δ 1.01 (d, 3H, J 7.2 Hz), 1.80-2.15 (m, 2H), 2.30 – 2.85(m, 6H), 2.86 (s, 3H), 3.35 (t, 1H, J 11.0 Hz), 3.58 (s, 3H), 3.59 (s, 3H), 2.86 (s, 3H), 4.33-4.40 (m,1H), 5.71 (d, 1H, J 3.0 Hz), 6.36 (dd, 1H, J 9.0, 3.0 Hz), 6.97 (t, 1H, J 7.6 Hz), 7.06 (d, 1H, J 8.8 Hz), 7.02 (t, 1H, J 7.5 Hz), 7.03 (dd, 1H, J 3.0, 9.0 Hz), the remaining 8 protons wereunresolved in the aromatic region between 7.2 and 7.8 ppm.stable-trans-2: 1H NMR (400 MHz, CDCl3) δ 0.70 (d, 3H, J 7.0 Hz), 1.80-2.15 (m, 2H), 2.30 – 2.85(m, 6H), 2.99 (d, 1H, J 11.5 Hz), 3.89 (s, 3H), 3.58 (s, 3H), 3.59 (s, 3H), 3.68 (dd, 1H, J 8.5, 11.0Hz), 4.25-4.33 (m, 1H), 6.15 (dd, 1H, J 8.5, 1.5 Hz), 6.25 (t, 1H, J 8.5 Hz), 6.97 (t, 1H, J 7.6 Hz),7.06 (d, 1H, J 8.8 Hz), 7.18 (t, 1H, 7.4 Hz), the remaining 7 protons were unresolved in the aromaticregion between 7.2 and 7.8 ppm.unstable-trans-2: 1H NMR (500 MHz, CDCl3) δ 1.09 (d, 3H, J 8.0 Hz), 1.77-2.00 (m, 2H), 2.0-2.8(m, 9H), 3.29 (t, 1H, J 11.0 Hz), 3.58 (s, 3H), 3.59 (s, 3H), 3.87 (s, 3H), 4.25-2.33 (m, 1H), 6.09 (dd,1H, J 8.0, 1.5 Hz), 6.23 (t, 1H, J 7.5 Hz), 6.88 (t, 1H, J 7.5 Hz), 6.93 (t, 1H, J 7.5 Hz), 7.16 (d,1H, J 8.5 Hz). 7.23 (t, 1H, 7.5 Hz), 7.32 (d, 1H, J 8.5 Hz), 7.35-7.47 (m, 2H), 7.52 (d, 1H, J 8.0Hz), 7.62 (d, 1H, J 8.5 Hz).The unidirectionality of the thermal isomerization process was confirmed by isolation of unstable-cis-2by careful flash chromatography (SiO2, pentane/EtOAc, 3.5/1) followed by heating the sample (at 60 able-cis-2.10
Materials and methods (surfaces)P-type Boron doped Si(100) wafers with a maximum resistivity of 10 ohm cm-1 were obtained fromSilicon Quest International (USA). HPLC [CAS 108-88-3] grade toluene used was of 99.8% purity, andwas purchased from Acros Organics (Belgium) and 40% hydrofluoric acid [CAS 7664-39-3] waspurchased from Merck, (Germany). HPLC grade toluene (Acros) was used as received, while the othersolvents were reagent grade chemicals, and were used without further purification. All water andaqueous solutions used with surfaces was doubly distilled and demineralized (Milli-Q, 18.0 MΩ). Allpreparations of silicon wafers for XPS (X-ray Photoemission Spectroscopy) were performed in an argonfilled glove bag to avoid contamination.Experimental Procedures for surface modificationAminopropyltriethoxysilane (APTES) monolayer on quartzQuartz microscope slides were cut into pieces (2x1 cm) so as to fit into measurement cell of UV/Vis andCD spectrometers. They were cleaned using a 3/7 ratio of 30% H2O2 in H2SO4 (Caution! This mixtureis extremely corrosive and reactive toward organics) at 70 C. These samples were then rinsed withcopious water, sonicated (2 x 1 min), rinsed with MeOH, 1/1 MeOH/toluene, toluene, then immersedinto a 2% solution of APTES in toluene for 1h. These samples were then rinsed with toluene, sonicated(2 x 30 s), then dried under vacuum at 60 C, and stored under inert atmosphere.SOONHNHSiSiO OOOOQuartzstable-(R)-(M)-4Stable-(R)-(M)-4 (Motor monolayer on quartz plates)Quartz plates functionalized with APTES were immersed into a 0.01 M solution of (R)-(M)-3 in CH2Cl2under inert atmosphere. iPr2EtN (10 eq with respect to acid chloride) was added, and the mixtureallowed to stand at rt for 24 h, or 48 h. These slides were then rinsed with CH2Cl2, sonicated in toluene(3 x 30 s) and dried under a flow of N2 (g). Irradiation of these samples was performed at 365 nm in anargon purged vessel.Circular dichroism (CD) spectroscopyAs with the solution experiments, CD spectra of the monolayers were recorded using a Jasco J715spectropolarimeter and a JASCO PFD-350S/350L Peltier-type FDCD attachment with a temperaturecontrol with a 1.0 cm cell by placing the modified quartz plate flush with the wall of the standard cellholder (1 cm x 1 cm) with the following conditions: speed 100 nm/min, response time, 1 s; bandwidth 111
nm (solution) or 10 nm (surface), noise reduction was carried out on the spectrum of stable-(R)-(M)-4.The spectrum of unstable-(R)-(P)-4 was the average of 50 scans, whereas the spectrum of stable-(R)(M)-4 was the average of 10 scans.-1.0-0.8-0.6-0.4 ength (nm)Figure S5: CD spectrum of (R)-(M)-4 (black) and (R)-(P)-4 (red).Since the CD signal observed for the monolayer was very low (as expected), many scans wererequired to obtain spectra with minimal no
Solution CD spectra were recorded using a Jasco J715 spectropolarimeter and a JASCO PFD- 350S/350L Peltier-type FDCD attachment with a temperature control with a 1.0 cm cell with the following conditions: speed 100 nm/mi
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L. Dai et al. 1152 ¹ 2003 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim www.chemphyschem.org CHEMPHYSCHEM 2003, 4, 1150 1169 example, BN, B xC yN z, GaP, GaAs), oxide nanotubes (for example, SiO 2,Al 2O 3,V 2O 5,TiO 2), and polymer nanotubes (for example, polyacrylonitrile, polyaniline,
May 2020 (FY 2020) France J2 1 France L1 2 France L2 4 France NATO2 14 Georgia A1 1 Georgia A2 1 Georgia B1/B2 1 Georgia H2B 1 Germany A1 12 Germany A2 6 Germany B1 3 Germany B1/B2 12 Germany C1 1 Germany C1/D 20 Germany G1 8 Germany G4 13 Germany H1B 1 Germany J1 5 Germany L1 4 Germany L2 2 Germany NATO2 43 Germany NATO6 8 Ghana B1/B2 2 Ghana .
of foodstuffs such as cheese, bread dough, and soy sauce or in alcoholic fermentation processes. In some Asian and Amer-ican cultures fungi have been used by cults as the source of . 38, 1328–1349 WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999 1433-7851/99/3810-1329 17.50 .50/0 1329. REVIEWS H. Sauter et al. Asteraceae.[3] This followed .
available in the Wiley Library (Wiley-VCH 2001 data software, Weinheim, Germany). Bacterial preparation. The lyophilized cultures of. L. monocytogenes . PTCC1165 were transferred into brain heart infusion (BHI) broth (Merck, Germany) and incubated at 37 C for 18 h, with two consecutive transfers. Bacterial sus -
2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Sodium Chloride GISBERT WESTPHAL, Solvay Salz GmbH, Solingen, Federal GERHARD KRISTEN, Solvay Salz GmbH, Solingen, Federal WILHELM WEGENER, S udwestdeutsche Salzwerke AG, Heilbronn, Germany PETER AMBATIELLO, Salzbergwerk Berchtesgaden, Germany HELMUT GEYER,
either obtained from the Caltech Mass Spectral Facility or an Agilent 6200 Series TOF with an Agilent G1978A Multimode source in electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI) or mixed (MM) ionization mode. Optical rotations were measured on either a Jasco P-1010
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