ライフサイエンスコーパス: H-atom abstraction

1 se ions react like typical diradicals (e.g., H atom abstractions).

2 th the aliphatic C-H bonds of amino acids by H atom abstraction.

3 ,6-tetramethylpiperidin-1-ol derivatives via H atom abstraction.

4 idate radicals, allowing their first use for H atom abstraction.

5 action with H atom donors proceed via direct H atom abstraction.

6 ze remarkably diverse reactions initiated by H-atom abstraction.

7 do unit contributes to the driving force for H-atom abstraction.

8 ilic substrate PPh3 but is not activated for H-atom abstraction.

9 te can direct the 5'-dAdo* toward productive H-atom abstraction.

10 e corresponding Co-imine complexes via alpha-H-atom abstraction.

11 iminyl radical was too slow to compete with H-atom abstraction.

12 ither retro-Bergman ring opening or external H-atom abstraction.

13 rmodynamically and kinetically competent for H-atom abstraction.

14 s 6 and 7 that also come from intermolecular H-atom abstraction.

15 C-C bond constructions, dehalogenations, and H-atom abstractions.

16 After the H-atom abstraction, a reasonable pathway for substrate h

17 is enzyme initiates its reaction by C(alpha) H-atom abstraction and is able to catalyze the formation

18 zed in the presence of this cluster both via H-atom abstraction and oxygenation with approximately 50

19 e enantioselectivity is dictated by both the H-atom abstraction and radical recombination steps due t

20 uted alpha-ketoamides proceed by competitive H-atom abstraction and sequential SET-desilylation pathw

21 tion that consists of enantiodifferentiative H-atom abstraction and stereoretentive radical substitut

22 0, which were all formed from intramolecular H-atom abstraction and trapping of the corresponding bir

23 tetradecane) are evaluated in hydrogen atom (H-atom) abstraction and oxo-transfer reactions.

24 de reactions such as alpha-deprotonation and H atom abstraction, and to facilitate enantioselective h

25 Rh(III)-H bond is weak, being susceptible to H atom abstraction as well as deprotonation.

26 330 nm, and tau = 50 ns) via intramolecular H-atom abstraction as the main photoreactivity of 3.

27 in k(cat) (approximately 3000-fold) support H-atom abstraction as the relevant substrate-activation

28 ylphosphine radical cations, which engage in H-atom abstraction as well as CH phosphoranylation.

29 of the sugar moiety that arise from initial H atom abstraction at the C5' position.

30 I, an Fe(IV)-Fe(IV) complex, followed by the H-atom abstraction at the transition state III leading t

31 ggest that the reaction proceeds through 1,5-H atom abstraction by a hydroxyl radical generated with

32 approximately 7) and strongly suggests that H atom abstraction by the peroxyl radical occurs with su

33 l to aldehyde equilibration involving formyl H-atom abstraction by a TEDA(2+) radical dication, decar

34 rimental and theoretical evidence for direct H-atom abstraction by ABLM and proposes an attractive me

35 fined by the NRVS data, show that the direct H-atom abstraction by ABLM is thermodynamically favored

36 Direct H-atom abstraction by ABLM would generate a reactive Fe(

37 proposed mechanism for LO catalysis involves H-atom abstraction by an FeIII-OH- site, best described

38 This result suggests that H-atom abstraction by benzophenone is rapid and that the

39 -TOH) enables tuning their reactivity toward H-atom abstraction by peroxyl radicals.

40 ic isotope effect (KIE) = 6, consistent with H-atom abstraction by S being the rate-determining step.

41 ce that bifurcation of radical rebound after H-atom abstraction can be driven both by the ability of

42 mechanisms of reaction initiated by toluene H-atom abstraction chemistry are detailed.

43 f 4-methyl-N-hydroxyphthalimide (4-Me-NHPI), H-atom abstraction competes with self-decomposition in t

44 spectra of isoleucine and leucine show that H-atom abstraction distal to the alpha-carbon occurs pre

45 step of all these processes, intramolecular H-atom abstraction efficiently intercepts the p-benzyne

46 ial and proton affinity contributions to the H-atom abstraction energy.

47 The pi-trajectory for H atom abstraction (Fe(IV) horizontal lineO oriented per

48 om N(2) extrusion, which mediates a proximal H-atom abstraction followed by a rapid C-O bond forming

49 nol led to formation of 5 via intermolecular H-atom abstraction followed by lactonization.

50 [k(H)/k(D) = 38.4(1)], suggesting a stepwise H-atom abstraction followed by radical recombination.

51 o produce nitrocatechols, one (equivalent to H atom abstraction) following fast electron transfer fro

52 Fe(III)-OOH is found to be more effective in H-atom abstraction for strong C-H bonds, while the highe

53 ion that Fe(III)-O2(-) species can carry out H atom abstraction from a C-H bond to initiate the 4-ele

54 Radical H atom abstraction from a set of N-heterocyclic carbene

55 by a direct reversal mechanism initiated by H atom abstraction from C-6 of the thymine dimer.

56 tion, there is a roughly 85:1 preference for H atom abstraction from C6 versus C7; however, this inve

57 comitantly, supposedly capable of the second H atom abstraction from C9.

58 mu-oxo)dicupric core is highly activated for H atom abstraction from CH(4).

59 H atom abstraction from CH2 sites, followed by a fission

60 resulting Cu(II)-O2(*-) is activated toward H atom abstraction from cysteine.

61 rs in addition to the intrinsic rate of C-4' H atom abstraction from DNA sugars.

62 h of these reactions are expected to involve H atom abstraction from each of two adjacent carbon cent

63 single spectrum permits the relative rate of H atom abstraction from each position to be determined.

64 as a demonstration of highly chemoselective H atom abstraction from electron-rich and relatively wea

65 )OOH)](2+); this is further substantiated by H atom abstraction from O-H substrates by [Cu(II)(2)(BPM

66 vity consistent with a minor contribution of H atom abstraction from the -OCH3 group to the overall r

67 ructural basis for direct and stereospecific H atom abstraction from the buried G(734) of pyruvate fo

68 enerate a Cu(II)-superoxo species capable of H atom abstraction from the peptidyl substrate, followed

69 n-and that homolysis of SAM concomitant with H atom abstraction from the substrate is readily reversi

70 rrous intermediate, formed by O(2)-activated H atom abstraction from the substrate, can exploit diffe

71 iperidin-1-yloxidanyl) resulted in immediate H- atom abstraction from the benzylic position of the ch

72 : dioxygenation of an indole derivative, and H-atom abstraction from an activated O-H bond.

73 s significantly stronger than the C7-H bond, H-atom abstraction from C4 is facilitated by H-bond form

74 coupled electron transfer), followed by (b) H-atom abstraction from LH by the Ag-coordinated F atom.

75 fferent NHC-boryl radicals were generated by H-atom abstraction from NHC-ligated trihydroborates.

76 studies indicate that C-H amidation involves H-atom abstraction from R-H substrates by nitrene interm

77 In contrast, H-atom abstraction from substrate by the side-on Cu(II)(

78 dition to the aminoxyl moiety of 4-O-TPO and H-atom abstraction from the 2- or 6-methyl groups or fro

79 osphoglycolate termini that are derived from H-atom abstraction from the 4'-position of the deoxyribo

80 rrect orientation and distal O character for H-atom abstraction from the ACV substrate.

81 generate a reactive Cu(II)/O(2) species for H-atom abstraction from the C-H bond of substrates.

82 3 is also formed via H-atom abstraction from the corresponding mu-1,1-hydrope

83 roxyl radical to the double bond followed by H-atom abstraction from the intermediate by another equi

84 ex containing an enamide ligand derived from H-atom abstraction from the PmIm chelate.

85 arrier of the initial (and rate-determining) H-atom abstraction from the stearoyl substrate as compar

86 orts the conclusion that cleavage occurs via H-atom abstraction from the sugar moieties, consistent w

87 The rate constants for H-atom abstraction from these substrates correlate well

88 Intramolecular hydrogen atom (H-atom) abstraction from the o-OCH3 group effectively in

89 IV)-oxo core remains highly reactive in both H atom abstraction (HAA) and O atom transfer (OAT) react

90 The rate-determining step involves H atom abstraction (HAA) from an organic substrate to ge

91 bound and dissociation mechanisms) following H-atom abstraction (HAA) from a substrate C-H bond by hi

92 isotope effect (KIE = 31.9 +/- 1.0) suggests H-atom abstraction (HAA) is the rate-determining step, i

93 ctive oxygen-centered radical 2b undergoes a H-atom abstraction (HAA) reaction with 1,4-cyclohexadien

94 N]Ni horizontal lineNAd (1), which undergoes H-atom abstraction (HAA) reactions with benzylic substra

95 er decay of [((Tr) L)Co(NC(6) F(5) )](2) via H-atom abstraction (HAA) reveals saturation kinetic beha

96 ously participate in intramolecular phenolic H-atom abstraction (HAA).

97 cal rebound hydroxylation at the site of the H-atom abstraction (HAA); however, recent reports have s

98 s and artificial catalysts are competent for H atom abstraction in catalytic cycles.

99 In this work we probed the specific role of H atom abstraction in HydG-catalyzed carbon monoxide and

100 ding the selectivity of S-oxygenation versus H atom abstraction in thiolate-ligated nonheme metalloen

101 tigate possible reactive Cu/O(2) species for H-atom abstraction in peptidylglycine alpha-hydroxylatin

102 substrates, whereas the transition state of H atom abstraction is destabilized, presumably due to a

103 H-atom abstraction is favored by a high E(o) of the FeII

104 nsity in terms of relative rate constants of H-atom abstraction (k(inh)) from the various tocopherol

105 ring opening, k(-1), and the intermolecular H-atom abstraction, k2, were determined from the depende

106 strate that TsrM does not catalyse substrate H-atom abstraction like most radical SAM enzymes.

107 dants, capable of activating C-H bonds by an H-atom abstraction mechanism.

108 lectivities are achieved by highly selective H atom abstraction of equatorially disposed alpha-hydrox

109 ions revealed that the reaction barriers for H-atom abstraction of cyclohexane by the ground state of

110 a reaction mechanism involving dibenzylamine H-atom abstraction or electron-transfer oxidation by the

111 nitiate diverse radical reactions via either H-atom abstraction or substrate adenosylation.

112 ed to undergo both intra- and intermolecular H-atom abstraction processes.

113 result of stabilization of the [Cu(2)OH](2+) H-atom abstraction product by electron delocalization ov

114 r distribution-and abundance relative to the H-atom abstraction products-changes in the presence of g

115 intermediate, caught in the act of substrate H-atom abstraction, providing new insights into the mech

116 c radical clock substrate support a stepwise H-atom abstraction/radical rebound pathway.

117 n a dichloromethane solution, the rate of an H atom abstraction reaction can be accelerated by a fact

118 e strong [Cu(2)OH](2+) bond formed along the H atom abstraction reaction coordinate.

119 The substrate H-atom abstraction reaction by the Cu(II)(M)-OOH interme

120 a significant effect on the energetics of a H-atom abstraction reaction by the Cu(II)(M)-OOH interme

121 e putative Cu(II)(M)-OOH intermediate in the H-atom abstraction reaction of PHM.

122 The radical 12 undergoes a H-atom abstraction reaction with 1,4-cyclohexadiene to y

123 frontier molecular orbitals involved in the H-atom abstraction reaction.

124 s, which would be a product of Cu(II)(M)-OOH H-atom abstraction reaction.

125 of the (hydroxo)iron(III) complex to undergo H atom abstraction reactions is the basis for its cataly

126 XYLO)(O(2)(*-))](2+) (1), as demonstrated in H atom abstraction reactions with certain phenolic ArO-H

127 I)-OOH complexes are found to perform direct H-atom abstraction reactions but with very different rea

128 H-atom abstraction reactions, which are essential proces

129 isms of O-O bond homolysis and electrophilic H-atom abstraction reactions.

130 shed fundamental thermochemical data for the H atom abstraction reactivity of dicopper(II) superoxo c

131 ar orbitals (FMOs) and their contribution to H atom abstraction reactivity.

132 trast to the behavior of LS Fe(III)-OOH, the H-atom abstraction reactivity of HS Fe(III)-OOH is found

133 Conversely, H-atom abstraction reactivity on an S = 2 surface allows

134 t phenyl nitrenium reacts through sequential H atom abstractions, resulting in the eventual formation

135 In addition to the expected H-atom abstraction, several unprecedented reaction pathw

136 data are consistent with an initial E(1) net H-atom abstraction step that furnishes the cis amide/amm

137 netic isotope effect (1.35 0.03) suggests an H-atom abstraction step with an asymmetric transition st

138 rizontal lineO unit is much more reactive at H-atom abstraction than its S = 1 counterpart and sugges

139 ished mechanism of autoxidation proceeds via H-atom abstraction through a cyclic network of peroxy-hy

140 rimary (N-demethylation) sp(3) C-H bonds via H atom abstraction to form dehydro- and desmethyl-ofloxa

141 on of a biradical species via intramolecular H atom abstraction to generate its lowest triplet ketone

142 , with a phenolic substrate, involving a net H-atom abstraction to cleave the bridging peroxo O-O bon

143 ted state decays by efficient intramolecular H-atom abstraction to form a 1,4-biradical, 8, that has

144 out this reaction via alpha-carbon (Calpha) H-atom abstraction to form a peptidyl Calpha radical tha

145 sitizer moiety, undergoes intramolecular 1,4-H-atom abstraction to form biradical 6, which was identi

146 bond into an alkyl chain by double hydrogen (H) atom abstraction using molecular O2.

147 e substrate can undergo different reactions (H-atom abstraction vs. electrophilic aromatic attack) wi

148 mpetition experiments, the rate constant for H atom abstraction was determined and found to be about

149 moted reactivity (e.g., nitrene transfer and H-atom abstraction), where the divergent reactivity is r

150 suggested by Aoyama, involves excited-state H-atom abstraction while the other, put forth by Whitten

151 mylation proceeds most likely via aldehyde C-H atom abstraction (Zhu, W.