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

4 ter group, in clear contrast to nonenzymatic silylations.

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

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

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

8 Silylation and desilylation are important functional gro

9 In situ silylation and enolization induces diastereoselective mi

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

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

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

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

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

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

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

17 Enantioselective silylations are performed with commercial silyl chloride

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

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

20 Silylation at low temperature gave predominantly monoary

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

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

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

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

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

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

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

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

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

30 Silylation chemistry on porous silicon provides for ultr

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

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

33 The reaction involves silylation, difluorocarbene addition using Me3SiCF2Br ac

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

49 2SiEt3](NCAr)]+ [BAr4]- (6), and associative silylation of 6 to release 3 and regenerate 4b.

50 Silylation of a hafnocene complex containing a strongly

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

74 Silylation of guanosine with 2 proceeded with excellent

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

104 Silylation of the zeolite increases hydrophobicity witho

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

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

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

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

109 Regioselective and enantioselective silylation of unsymmetrical substrates was also achieved

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

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

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

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

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

115 The silylation proceeds under mild conditions, in the absenc

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

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

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

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

120 SO2Py allows for further elaboration of the silylation products.

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

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

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

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

125 veal key intermediates and byproducts of the silylation reaction.

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

127 Classical silylation reactions often suffer from poor functional g

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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