ライフサイエンスコーパス: silylation

1 fication by enzymatic sulfate removal and/or silylation).

2 tionalizaton is illustrated by electrophilic silylation.

3 tely resulting in a redox-neutral alkylation/silylation.

4 -block metals, and new examples of reductive silylation.

5 th conservation of the ee value from the C-H silylation.

6 ter group, in clear contrast to nonenzymatic silylations.

7 e acetal, SPA) that rapidly isomerizes via C-silylation accompanied by an O-desilylation to the alpha

8 ilylation of benzylicsilyl ethers; the ortho-silylation activity of the bpy-UiO-Ir is at least 3 orde

9 Subsequent reductive desulfonylation/silylation afforded N-difluoro(trimethylsilyl)methyl-1,2

10 endo oxo out of the cone, whereupon a second silylation affords the stable U(IV) cis-bis(siloxide) [A

11 In particular, a one-pot tandem alkyne silylation/allylic substitution sequence, in which both

12 Rates of isothiourea catalyzed silylation and acylation reactions were measured for sub

13 ctions, including chemoselective borylation, silylation and amination of benzylic C-H bonds, as well

14 ification of materials via processes such as silylation and atomic layer deposition.

15 Analogous electron-catalyzed silylation and borylation are also demonstrated with qui

16 provide a picture of the state of art of the silylation and borylation of C-H bonds as applied to the

17 d methods for the transition-metal-catalyzed silylation and borylation of C-H bonds have led to their

18 Although the silylation and borylation of C-H bonds have undergone ex

19 pplication of the transition-metal-catalyzed silylation and borylation of C-H bonds to the synthesis

20 nt the rapid development of enantioselective silylation and borylation of C-H bonds, with an emphasis

21 Silylation and desilylation are important functional gro

22 In situ silylation and enolization induces diastereoselective mi

23 l protected ribonolactone) after consecutive silylation and fluorination cycles.

24 nt compounds in concise sequences comprising silylation and functionalization.

25 d through a combination of reduction and oxo-silylation and migration from a trans to a cis position,

26 th strong implications in both catalytic C-H silylation and olefin hydrosilylation.

27 sp(3))-H oxidation and a directed C(sp(3))-H silylation and oxidation provides rapid access to highly

28 oducts in rapid reactions but also triggered silylation and reductive halobenzylation as secondary tr

29 ated by sequential C(sp(3))-H and C(sp(2))-H silylations and functionalizations, as well as diastereo

30 -catalyzed condensation with formaldehyde, O-silylation, and Cu(I)-promoted 1,4-addition of isopropyl

31 none carbonyl functionality, dehydrogenative silylation, and deoxygenative cyclization of chalcones t

32 owever, the pathway through which reduction, silylation, and migration occurred was unknown.

33 ate additions, carbonylations, methylations, silylations, and brominations.

34 Mechanistic aspects of the silylation are discussed, and the application of the pro

35 The products of this silylation are suitable for subsequent oxidation, haloge

36 Enantioselective silylations are performed with commercial silyl chloride

37 as well as the number of methoximations and silylations are used as search constraints.

38 l with diethylsilane, undergo regioselective silylation at a secondary C-H bond gamma to the hydroxyl

39 Silylation at low temperature gave predominantly monoary

40 omoarenes underwent efficient metalation and silylation at low temperature to provide aryl siloxanes.

41 niline with diethylsilane, undergo selective silylation at the C-H bond gamma to the amino group.

42 e mechanism and origin of selectivity in our silylation-based kinetic resolution.

43 standing of the origin of selectivity in our silylation-based kinetic resolutions and a role the phen

44 nt p-substituted triphenylsilyl chlorides on silylation-based kinetic resolutions was explored.

45 lation of diphenylketene is preferred over C-silylation by 5.4 kcal/mol in the gas phase.

46 s show that C-silylation is preferred over O-silylation by 8.2 kcal/mol.

47 ion onto the remaining alkene and subsequent silylation by a sigma-bond metathesis reaction, affordin

48 )O(11)(OH)}UO(2)], which undergoes rapid oxo silylation by HN(SiMe(3))(2), followed by silyloxy ligan

49 Indole C-H silylation can preferentially occur at the nucleophilic

50 e highest turnover number of any Fe-based N2 silylation catalyst to date (up to 65 equiv N(SiMe3)3 pe

51 hly enantioselective intermolecular C-H bond silylation catalyzed by a phosphoramidite-ligated iridiu

52 Silylation chemistry on porous silicon provides for ultr

53 ermolecular condensation and dehydrogenative silylation-deoxygenative intramolecular cyclization casc

54 sis of the three extracts by GC/MS using the silylation derivatization technique revealed 53 compound

55 ed by comparison of conventional and in situ silylation, developed for space research applications, u

56 The reaction involves silylation, difluorocarbene addition using Me3SiCF2Br ac

57 Calculations confirm that only one silylation event is needed to initiate oxo rearrangement

58 e)](2) leads to highly selective cyclization/silylation events.

59 lyzed conjugate addition followed by enolate silylation for the synthesis of beta-disubstituted silyl

60 SPD) prior to their determination by on-line silylation gas chromatography tandem mass spectrometry (

61 ectly by 1H and 13C multidimensional NMR and silylation GC-MS.

62 ed organophotoredox-catalyzed regioselective silylation/germylation-radical cascade cyclization of 1,

63 ation of diphenylketene leads to exclusive C-silylation giving the diphenyl(triethylsilyl)acetyl cati

64 yl ethers undergo Csp2-H and benzylic Csp3-H silylation in a single vessel.

65 indole, and N-methyl-5-bromoindole underwent silylation in good yield, whereas a low yield of siloxan

66 taining sensitive functional groups, undergo silylation in high yield for the first time, and arenes

67 ne or its derivatives undergo asymmetric C-H silylation in high yield with excellent enantioselectivi

68 he first experimental proof of the course of silylation in the McKenna reaction, one of the most wide

69 alysis, where rate-determining bound amidate silylation is activated by the metal center and influenc

70 Catalytic C-H bond silylation is facile with partially fluorinated aromatic

71 only the unencapsulated exo oxo and only one silylation is needed to enable migration of the endo oxo

72 y functional theory calculations show that C-silylation is preferred over O-silylation by 8.2 kcal/mo

73 Chemical derivatization, especially silylation, is widely used in gas chromatography coupled

74 The steps of the silylation mechanism may follow either an ionic route in

75 direct glycosylation using the Vorbruggen's silylation method and provided exclusively the beta-anom

76 elopment of efficient and broadly applicable silylation methodologies remains a central goal in synth

77 conducive to reaction at the enolic oxygen (silylation, methylation, allylation, and acylation).

78 ulfido complexes to avoid autoreduction, and silylation models protonation.

79 The silylation occurs with high selectivity at a secondary C

80 2SiEt3](NCAr)]+ [BAr4]- (6), and associative silylation of 6 to release 3 and regenerate 4b.

81 Sequential reduction and silylation of a formally diiron(I) bridging CO complex u

82 Silylation of a hafnocene complex containing a strongly

83 jugated system and those driven by selective silylation of a particular isomer.

84 key to this coupling reaction is the partial silylation of a reduced iron-dinitrogen complex, followe

85 The efficient silylation of alcohols with di- and trialkynylsilanes wa

86 interactions to enable substrate-selective O-silylation of ammonium alcohols over more reactive aliph

87 the alkene followed by iridium-catalysed C-H silylation of an unactivated delta-C(sp(3))-H bond to pr

88 itative calculations showed that the partial silylation of anhydrosugars was almost completely overco

89 Mechanistic studies on the rhodium-catalyzed silylation of arene C-H bonds are reported.

90 We report a Rh-catalyzed, enantioselective silylation of arene C-H bonds directed by a (hydrido)sil

91 and versatile system that shows (reversible) silylation of arenes and heteroarenes as well as reducti

92 henanthroline (2,9-Me(2)-phen) catalyzes the silylation of arenes at lower temperatures and with fast

93 defines a cycle for the catalytic direct C-H silylation of arenes.

94 d)(OMe)](2) form complexes that catalyze the silylation of aromatic and aliphatic C-H bonds.

95 potassium tert-butoxide catalyses the direct silylation of aromatic heterocycles with hydrosilanes, f

96 an the previously reported rhodium-catalyzed silylation of aryl C-H bonds and occurs with a wide rang

97 by the H(2) byproduct is shown to limit the silylation of aryl C-H bonds in the presence of the most

98 A method for the iridium-catalyzed silylation of aryl C-H bonds is described.

99 is method converts arylsilanes formed by the silylation of aryl C-H bonds to trifluoromethylarenes, t

100 We report a new system for the silylation of aryl C-H bonds.

101 es on the mechanism of the iridium-catalyzed silylation of aryl C-H bonds.

102 s on the rhodium-catalyzed, enantioselective silylation of aryl C-H bonds.

103 The scope of the palladium-catalyzed silylation of aryl halides with triethoxysilane has been

104 We report an unprecedented catalytic ipso-silylation of aryl methyl ethers under mild conditions a

105 tivated precursors based on Ru-catalyzed C-H silylation of arylboronates.

106 that allows for the site-selective sp(2) C-H silylation of azines is described.

107 aldehydes followed by dehydrogenative ortho-silylation of benzylicsilyl ethers as well as C-H boryla

108 using B2(pin)2 (pin = pinacolate) and ortho-silylation of benzylicsilyl ethers; the ortho-silylation

109 nes while the BB monomers were obtained from silylation of bisphenols by t-butyldimethylsilyl chlorid

110 nds are highly active for the borylation and silylation of C-H bonds, but chiral analogs of these cat

111 ach to catalytic reductive Csp2-H and Csp3-H silylation of carboxylic acid derivatives encompassing e

112 ylsilane, undergo asymmetric, intramolecular silylation of cyclopropyl C-H bonds in high yields and w

113 rs, generated in situ by the dehydrogenative silylation of cyclopropylmethanols with diethylsilane, u

114 the B3LYP/6-311+G* level indicate that the O-silylation of diphenylketene is preferred over C-silylat

115 odesilylation, was found to initiate the C-H silylation of electron-rich (hetero)arenes with hydrosil

116 We report that the silylation of five-membered-ring heteroarenes occurs wit

117 Silylation of guanosine with 2 proceeded with excellent

118 In this context, the C-H silylation of heteroarenes is a topic of intense interes

119 ew method for the direct dehydrogenative C-H silylation of heteroaromatics utilizing Earth-abundant p

120 Another possible reaction pathway includes silylation of imidazolide anion at the N-3 atom, followe

121 general strategy for the regioselective C7-H silylation of indole derivatives.

122 Dehydrogenative silylation of internal olefins such as cis- and trans-4-

123 H3N), promotes the catalytic dehydrogenative silylation of linear alpha-olefins to selectively form t

124 These results exemplify the catalytic silylation of N(2) by a synthetic metal-sulfur cluster a

125 h is shown to facilitate catalytic reductive silylation of N(2) with turnover numbers far exceeding t

126 ey N-C bond forming step occurs upon partial silylation of N(2).

127 Here, we report that the silylation of oxidized porous silicon offers a DIOS plat

128 oup tolerance and facilitating the efficient silylation of pharmaceutically relevant molecules.

129 l orthogonal cross-couplings, and late-stage silylation of phenolic bioactive molecules and BINOL sca

130 cting group strategy for catalytic ortho-C-H silylation of phenols was also successfully applied to p

131 The materials were prepared by silylation of porous silica gel with monochlorosilane de

132 ridium-catalyzed, regio- and stereoselective silylation of primary and secondary C(sp(3))-H bonds in

133 d practical Pd(II) -catalyzed intermolecular silylation of primary and secondary C-H bonds of alpha-a

134 s only 40-50 times slower than the analogous silylation of primary C-H bonds.

135 Reaction rates for the base-catalyzed silylation of primary, secondary, and tertiary alcohols

136 Herein we report the copper-catalyzed silylation of propargylic difluorides to generate axiall

137 We report Ir-catalyzed intramolecular silylation of secondary alkyl C-H bonds.

138 alcohols or ketones to anti-1,3-diols by the silylation of secondary C-H bonds gamma to oxygen and ox

139 The silylation of secondary C-H bonds in secondary silyl eth

140 This silylation of secondary C-H bonds is only 40-50 times sl

141 chemoselective and regioselective late-stage silylation of small heterocycles, including drugs and dr

142 eveloped that allows catalytic reductive C-H silylation of sterically hindered phenols.

143 Copper(II)-catalyzed silylation of substituted alkynylcarbonyl compounds was

144 As a consequence, the selectivity of the silylation of substituted arenes is generally governed b

145 ligand for enantioselective, intramolecular silylation of symmetrical diarylmethoxy diethylsilanes.

146 mic force microscopy, confirms the reductive silylation of synthetic carbon allotropes as a new coval

147 tbpy) catalyzes the Z-selective, dehydrative silylation of terminal alkenes, but not 1,2-disubstitute

148 dditive-free Mn(I)-catalyzed dehydrogenative silylation of terminal alkenes.

149 A rapid and high-yielding silylation of terminal alkynes employing TMSOTf and cata

150 The Cu-catalyzed silylation of terminal and internal alkynes bearing a 2-

151 ed to minimize these problems, including the silylation of the active OH groups within the surface of

152 gh borylation of the allenamide, followed by silylation of the alkyne and then reductive elimination,

153 rein is an iridium-catalyzed, regioselective silylation of the aromatic C-H bonds of benzylamines and

154 namide with halomethylsilanes and subsequent silylation of the C(sp(3))-H bonds with broad scope.

155 s protocol describes a method for the direct silylation of the carbon-hydrogen (C-H) bond of aromatic

156 The second step is based on silylation of the ester compounds using bis(trimethylsil

157 le: weakening upon N2 binding, breaking with silylation of the metal-bound N2 and reforming with expu

158 After silylation of the O(2)-carbonyl with TMSCl, the N(6)-ami

159 This drastically increased the complete silylation of the pyrolysis products and the chromatogra

160 method also employs solid-phase extraction, silylation of the solvent extract, and analysis by gas c

161 Silylation of the U(VI) oxo groups by bis(trimethylsilyl

162 General reductive silylation of the UO2(2+) cation occurs readily in a one

163 ual reactivity centered around the reductive silylation of the uranyl ion which entailed conversion o

164 Silylation of the zeolite increases hydrophobicity witho

165 -assisted method for the regioselective para silylation of toluene derivatives.

166 A Cu-catalyzed carbonylative silylation of unactivated alkyl halides has been develop

167 re, we report a catalytic intermolecular C-H silylation of unactivated arenes that manifests very hig

168 A Ni/Cu-catalyzed silylation of unactivated C-O electrophiles derived from

169 s are ongoing, we propose that CuH-catalyzed silylation of unsaturated acids occurs to access a uniqu

170 Regioselective and enantioselective silylation of unsymmetrical substrates was also achieved

171 lizations, as well as diastereoselective C-H silylations of a chiral, natural-product derivative cont

172 Several classes of enantioselective silylations of C-H bonds have been reported recently, bu

173 orresponding aziridines by primary-selective silylations of four azido diols, mesylations, and reduct

174 port highly enantioselective intramolecular, silylations of unactivated, primary C(sp(3))-H bonds.

175 tinjection methylation reaction, rather than silylation or acetylation, was used to form a volatile d

176 ctionalization of C-H bonds is the catalytic silylation or borylation of C-H bonds, which enables a b

177 operationally simple, rapid, and economical silylation platform based on trifluoromethyltrimethylsil

178 The silylation proceeds under mild conditions, in the absenc

179 Enantioenriched benzoxasiloles from the silylation process undergo a range of transformations to

180 n the preferred pathway of this directed C-H silylation process.

181 idate the mechanism of this beta-C(sp(3) )-H silylation process.

182 lineCHSiMe3)2 (1b) exclusively forms the C-H silylation product C6F5SiMe3 with ethylene as a byproduc

183 ; the reductive elimination step to form the silylation product is much slower than reductive elimina

184 SO2Py allows for further elaboration of the silylation products.

185 The silylation reaction is shown to be reversible, with an e

186 similarities between the borylation and the silylation reaction mechanisms enabled us to considerabl

187 veal key intermediates and byproducts of the silylation reaction.

188 three isochalcogenourea catalysts in a model silylation reaction.

189 r the inherent nucleophilicity in an alcohol silylation reaction.

190 ctivities of different (hetero)arenes in the silylation reaction.

191 l ionic intermediates present during the C-H silylation reaction.

192 Traditionally, silylation reactions employ chlorosilanes or hydrosilane

193 logs of these catalysts for enantioselective silylation reactions have not been developed.

194 ategy proved to be general in various alkene silylation reactions including disilylation, hydrosilyla

195 talyzed syn-selective 1,2-carboboration and -silylation reactions of alkenes containing cleavable dir

196 The silylation reactions of the AA were executed with N,O-bi

197 Classical silylation reactions often suffer from poor functional g

198 catalyst for Baylis-Hillman, acylation, and silylation reactions with good reactivity, product selec

199 The silylation reactions with these catalysts produce high y

200 ibiting orthogonal reactivity with classical silylation reactions.

201 otopically light and heavy (D6) forms of the silylation reagent N-methyl-N-tert-butyldimethylsilyl)tr

202 We found that the probase also acts as a silylation reagent, generating silyl enol ether or silyl

203 rcial or in situ-generated, were used as the silylation reagents, and a broad range of simple and fun

204 surface of the silica using amine-containing silylation reagents.

205 reductive ester or reductive ketone/aldehyde silylation, respectively.

206 The two labs used the same silylation sample preparation protocols but different in

207 riety of transformations (acylation, S(N)Ar, silylation, solvolysis, Pd catalyzed C-S cross-coupling

208 We demonstrated that this catalytic C-H bond silylation strategy has powerful synthetic potential by

209 cations of this transformation in orthogonal silylation techniques as well as in further derivatizati

210 Current competing methods for C-H bond silylation tend to be incompatible with functionalities,

211 served despite its inability to catalyze C-H silylation; the reductive elimination step to form the s

212 )(5) ][Fe(2) (CO)(2) L] (3), which undergoes silylation to Fe(2) (CO)(COSiMe(3) )L (4).

213 quivalents of Me3SiI results in stepwise oxo silylation to form (Me3SiO)2UI2((Mes)PDI(Me)) (5) or (Me

214 an capture a N(2) molecule and catalyse N(2) silylation to form N(SiMe(3))(3) under treatment with ex

215 cted aniline and phenol derivatives) undergo silylation to form the corresponding aryltriethoxysilane

216 he protein's chemoselectivity from preferred silylation to preferred amination of a substrate contain

217 ord silyl acetals and Rh-catalyzed ortho-C-H silylation to provide dioxasilines.

218 g disilylation, hydrosilylation, and allylic silylation under simple and transition-metal-free condit

219 s spectrometry of carbohydrates with in situ silylation using hexamethyldisilazane is presented in th

220 talysed intermolecular carbon-hydrogen (C-H) silylation using rhodium or iridium complexes in the pre

221 A dicobalt complex catalyzes N2 silylation with Me3SiCl and KC8 under 1 atm N2 at ambien

222 or the first time, and arenes that underwent silylation with prior catalysts react over much shorter