ライフサイエンスコーパス: homolytic

1 d-dissociation energies (BDE >94 kcalmol for homolytic, 1H --> H + 1, vs. approximately 127 kcalmol f

2 n this reaction are generated via the direct homolytic activation of alcohol O-H bonds in an unusual

3 proton-coupled electron transfer can enable homolytic activation of common organic functional groups

4 h enzymatic and oxidative reactions, via the homolytic addition of nitrogen dioxide to a double bond

5 rization of sulfoxides that does not involve homolytic alpha-cleavage chemistry.

6 Comparison of homolytic and heterolytic bond dissociation for tricoord

7 rgies for this pathway are favored over both homolytic and heterolytic O-O bond cleavage.

8 or criteria allowing the distinction between homolytic and heterolytic pathways in nondestructive met

9 als were used to determine 11 of 12 possible homolytic and heterolytic solution Co-H bond dissociatio

10 ceed through KO(t)Bu-promoted intramolecular homolytic aromatic substitution (HAS).

11 ms that can use a photoinduced base-promoted homolytic aromatic substitution reaction (photo-BHAS) ha

12 actions (SRN1-type chemistry), base-promoted homolytic aromatic substitutions (BHAS), radical Heck-ty

13 olecules (MSE) and of the radicals formed by homolytic bond cleavage (RSE) and their effect on BDE ar

14 xt step, demethylation of the sulphoxide via homolytic bond cleavage leads to methyl radical formatio

15 complished by taking advantage of the facile homolytic bond cleavage of the fragile Si horizontal lin

16 ments suggest that the U-Pn bonds degrade by homolytic bond cleavage, whereas the more redox-robust t

17 uced changes in the net forward rate of C-Co homolytic bond cleavage.

18 lowed by a SET-type C-Hal activation through homolytic bond cleavage.

19 The homolytic bond dissociation energies (BDEs(O-H)) for the

20 These calculations reveal that W-H homolytic bond dissociation energies (BDEs) decrease wit

21 The homolytic bond dissociation energies (BDEs) for the acid

22 On the basis of the homolytic bond dissociation energies (BDEs) only, the (a

23 Comparison of the C-F and C-Cl homolytic bond dissociation energies suggests that an im

24 The calculated adiabatic homolytic bond dissociation energy of this strained bond

25 The computed Co-C homolytic bond dissociation enthalpies (BDEs) of the lat

26 auling specified, describes quite accurately homolytic bond dissociation enthalpies of common covalen

27 y iodotyrosine results in loss of iodine via homolytic bond dissociation.

28 olycyclic aromatic intermediates, as well as homolytic bond fragmentation of the edge functional grou

29 erent reaction types involving hydrocarbons (homolytic C-C bond breaking of alkanes, progressive inse

30 end groups), dissociation starts with random homolytic C-C bond cleavages along the PS chain, which l

31 tion (CAD) of [M + Ag](+) starts with random homolytic C-C bond cleavages in the PS chain, which gene

32 hanism of the photoinduced uncaging involves homolytic C-C bond fragmentation followed by radical dis

33 bined in a thermodynamic cycle to afford the homolytic C-H bond dissociation energy.

34 that an electrophilic iron carbene mediates homolytic C-H cleavage and rebounds from the resulting o

35 Homolytic C-H dissociation prevails on bare (*-*) and O*

36 f neutral nitric oxide through a first-order homolytic C-N bond scission to release up to 88% nitric

37 , cinnamyl, and diarylmethyl, undergo facile homolytic C-N bond scission under mild conditions to giv

38 rgy by a diphenyl ether substrate results in homolytic C-O bond cleavage followed by recombination to

39 o an ion-pair intermediate that will undergo homolytic C-O bond cleavage via an approximately 11.0 kc

40 ciation chemistry is observed, including the homolytic C-S cleavage in (+3) charge state and various

41 The putative homolytic chemistry was confirmed by using 2-methyl-1-ph

42 Photodissociation with 266 nm light yields homolytic cleavage at the modification site, generating

43 ch the cofactor's Co-C bond is activated for homolytic cleavage may be operative for all base-off/His

44 The reaction was found to follow a homolytic cleavage mechanism as verified by electrospray

45 migration for extradiol cleavage and an O-O homolytic cleavage mechanism for intradiol cleavage.

46 ketoheptan-1-ol, also consistent with an O-O homolytic cleavage mechanism, and not consistent with a

47 Asn, Glu, Asp, or Lys residues augmented the homolytic cleavage of 8R-HPODE with formation of 10-hydr

48 l hydrogen atom transfer reactions, in which homolytic cleavage of a C-H bond is accomplished by a si

49 inactivation of P450 by aldehydes occurs via homolytic cleavage of a peroxyhemiacetal intermediate to

50 tion by those aldehydes apparently occurs by homolytic cleavage of a peroxyhemiacetal intermediate to

51 lsilyl radical may be initially generated by homolytic cleavage of a weakened Si-H bond of a hypercoo

52 reaction with aerobic, aqueous photoinduced homolytic cleavage of adenosylcobalamin, indicating that

53 We report ammonia oxidation by homolytic cleavage of all three H atoms from a [Mo-NH3](

54 istribution due to a high-energy barrier for homolytic cleavage of an exo bond in the intermediate cy

55 The radicals generated by the homolytic cleavage of an X-H bond from the guanine.cytos

56 basis of this evidence, it was proposed that homolytic cleavage of C-H bonds for CH(3)CN and CH(3)OH

57 function by radical mechanisms involving the homolytic cleavage of C-H or C-C bonds, i.e., biotin syn

58 ade, whereas Fenton catalysis results in the homolytic cleavage of H(2)O(2) producing free radicals t

59 A reversible bond dissociation enthalpy for homolytic cleavage of Me-Cbl is calculated as 31 +/- 2 k

60 r while longer wavelengths of light initiate homolytic cleavage of metal-carbon bonds that, after int

61 defined with respect to the heterolytic and homolytic cleavage of O-O bonds.

62 dical (GS*), a reaction product derived from homolytic cleavage of S-nitrosoglutathione (GSNO).

63 deprotonation of radical cation, followed by homolytic cleavage of the alcohol OH group from the phen

64 ylium radical 1(*+) which is generated via a homolytic cleavage of the B-B bond of 3.

65 and inactivation by 12-IODE is initiated by homolytic cleavage of the C(11)-H bond.

66 radicals on neutral tyrosine side chains by homolytic cleavage of the C-I bond.

67 from Lactobacillus leichmannii catalyzes the homolytic cleavage of the carbon-cobalt bond of adenosyl

68 The homolytic cleavage of the Co(III)-Ado or Co(III)-Me bond

69 Thermal treatment of the oxidized MOF causes homolytic cleavage of the Co(III)-halogen bonds, reducti

70 Visible light excitation induced homolytic cleavage of the Co-C bond and the formation of

71 Homolytic cleavage of the Co-C bond of anAdoCbl at the a

72 f the activating monocation to stimulate the homolytic cleavage of the Co-C5' bond in adenosylcobalam

73 adenosylcobalamin (coenzyme B12) results in homolytic cleavage of the Co-C5' bond, forming cob(II)al

74 Homolytic cleavage of the cobalt-carbon bond of the anal

75 ns, the 5'-deoxyadenosyl radical arises from homolytic cleavage of the cobalt-carbon bond, and it ini

76 bl-dependent enzymes accelerate the rate for homolytic cleavage of the cofactor's Co-C bond by approx

77 cobalamin, AdoCbl)-dependent enzymes promote homolytic cleavage of the cofactor's Co-C bond to initia

78 in each case catalysis is initiated through homolytic cleavage of the cofactor's Co-C bond.

79 Absorption at naphthalene causes homolytic cleavage of the connecting carbon-sulfur bond

80 the chemistry proceeds by rate limiting Cu-O homolytic cleavage of the Cu(II)-(OOH) species, followed

81 ity, suggesting that Asn(964) may facilitate homolytic cleavage of the dioxygen bond of 9R-HPODE with

82 nction as a sensitizer, thereby facilitating homolytic cleavage of the ditin reagent.

83 e formation of the oxon derivative, and (ii) homolytic cleavage of the N-C and C-S bonds of the organ

84 trong evidence of a grafting mechanism where homolytic cleavage of the N2(+) species occurs together

85 anism I, and the Ni-C bond length suggests a homolytic cleavage of the Ni(III)-methyl bond in the sub

86 The nonconcerted process involving homolytic cleavage of the O-N bond in 5 was found to be

87 late ligand of the diiron centre may trigger homolytic cleavage of the O-O bond by transferring a pro

88 t the hydroxylation reaction is initiated by homolytic cleavage of the O-O bond in the C(4a)-hydroper

89 The observed homolytic cleavage of the O-O bond of 1 is explored with

90 tudies revealed that I435 is not formed upon homolytic cleavage of the O-O bond of PN, but instead ar

91 Importantly, there is a barrier for homolytic cleavage of the O-O bond on the high-spin pote

92 ough an iron(III)-bound peroxynitrite before homolytic cleavage of the O-O bond to form an iron(IV)-o

93 Homolytic cleavage of the O-O bond yields the catalytica

94 ystems show similar reactivities and undergo homolytic cleavage of the O-O bond.

95 p in the thermal decomposition of PPE is the homolytic cleavage of the oxygen-carbon bond.

96 the metal, a process triggered by an unusual homolytic cleavage of the peroxide bond, forming a disto

97 te fragmentation of the ozonide initiated by homolytic cleavage of the peroxide bridge followed by re

98 Homolytic cleavage of the pyrrole NH leads to the format

99 roteins generate an adenosyl radical via the homolytic cleavage of the S-C(5') bond of SAM.

100 particular, hyper-long Co-N bonds may favor homolytic cleavage of the trans-cobalt-carbon bond in th

101 imately 10(12)-fold rate acceleration of the homolytic cleavage of the upper axial cobalt-carbon bond

102 rged as a major biochemical strategy for the homolytic cleavage of unactivated C-H bonds.

103 ails are explored by DFT supporting a simple homolytic cleavage pathway from a kappa(1)-ONO bound int

104 artitions between Calpha-Cbeta oxidation and homolytic cleavage pathways.

105 ation of a stable radical (by abstraction or homolytic cleavage reactions) increases the acidity of a

106 s, which then undergoes both heterolytic and homolytic cleavage to form iron(IV) pi-radical cations a

107 cating that a Cu(I)OOH species undergoes O-O homolytic cleavage to yield a hydroxyl radical and Cu(II

108 re calculated for three different reactions: homolytic cleavage via traditional Fenton chemistry, het

109 tions, 1,4-dihydropyridines (DHPs) undergo a homolytic cleavage, forming exclusively a Csp(3)-centere

110 ture, which may be important in facilitating homolytic cleavage, is the long cobalt-nitrogen bond lin

111 a number of possible pathways including O-O homolytic cleavage, M-O homolytic cleavage, nucleophilic

112 thways including O-O homolytic cleavage, M-O homolytic cleavage, nucleophilic O-atom transfer, and el

113 *)Cys) was the radical-directed Calpha-Cbeta homolytic cleavage, resulting in the formation of glycyl

114 d tert-butyl hydroperoxide, t-BuOOH) undergo homolytic cleavage.

115 n rearrangement, but not able to undergo O-O homolytic cleavage.

116 -chlorophenol, via a mechanism involving O-O homolytic cleavage.

117 at one mass unit above the mass expected for homolytic cleavage.

118 al (5'-dAdo*), the same radical generated by homolytic Co-C bond cleavage in B12 radical enzymes.

119 sts possess nearly identical heterolytic and homolytic Co-H bond strengths for the Co(III)H and Co(II

120 operoxides by a heterolytic path, although a homolytic course is likely taken in converting the norma

121 Homolytic decomposition of lipid hydroperoxides gives ri

122 C-mediated or transition metal ion-mediated homolytic decomposition of polyunsaturated omega-3 lipid

123 It undergoes homolytic decomposition to the DNA-reactive bifunctional

124 icosatetraenoic acid (15(S)-HPETE) undergoes homolytic decomposition to the DNA-reactive bifunctional

125 ifferent reaction catalyzed by the enzyme, a homolytic dehydration of the hydroperoxide to produce th

126 Their homolytic dissociation are however facile.

127 For all types of P-P bond discussed, homolytic dissociation is favored over heterolytic disso

128 s involving Ni(III) complexes generated from homolytic dissociation of disulfides/peroxides or halide

129 where the O...O bond is found to cleave via homolytic (Fe(IV) horizontal lineO) or heterolytic (Fe(V

130 h organic radical intermediates generated by homolytic fission of coenzyme's unique cobalt-carbon bon

131 e by a 5'-deoxyadenosyl radical generated by homolytic fission of the coenzyme cobalt-carbon bond.

132 h organic radical intermediates generated by homolytic fission of the coenzyme's unique cobalt-carbon

133 acid (HO-N=N-OH) with a concomitant azo-type homolytic fission of the latter to N2 and.OH.

134 cid (HO-N=N-OH; 3) with concomitant azo-type homolytic fission to N(2) and *OH.

135 ng ab initio/DFT methods, we identified five homolytic fissions of C-C and C-O bonds and five hydroge

136 Homolytic fragmentation of a hydroxyethylhydrazine radic

137 and a disulfide bond leads to excited state, homolytic fragmentation of the disulfide bond.

138 -N2)[Mo(N[t-Bu]Ar)3]2, 2, and the product of homolytic fragmentation of the NN bond, NMo(N[t-Bu]Ar)3,

139 Br (nor=1-bicyclo[2.2.1]hept-1-yl) and their homolytic fragmentations were studied computationally us

140 , we report an accurate determination of the homolytic gas-phase Co-C bond dissociation energies in t

141 pK(a) values were used to determine both the homolytic ([HPd(diphosphine)(2)](+) --> [Pd(diphosphine)

142 h the scissile C-H bond energy, indicating a homolytic hydrogen abstraction transition state.

143 d that the F429H mutant of CYP 2B4 undergoes homolytic instead of heterolytic O-OH bond cleavage.

144 rmation of a single product arising from the homolytic loss of CO followed by combination of the inte

145 This observation strongly supports a homolytic mechanism for O-O bond cleavage.

146 h a radical scavenger TEMPO do not support a homolytic mechanism.

147 turing reactive N-H bonds and estimate their homolytic N-H bond enthalpies (BDEN-H) via redox and aci

148 does not release NO radical via spontaneous homolytic N-NO bond fission nor freely diffuse through c

149 Mechanism for the homolytic N-O bond cleavage for acid generation was supp

150 The same homolytic nitro-carbon fragmentation can be diverted by

151 ial bridging peroxide intermediate undergoes homolytic O--O bond cleavage generating a trans heme/non

152 ound I (Cpd I), in a mechanism that involves homolytic O-O bond cleavage followed by H-abstraction fr

153 d, (HPX-CO2H)FeIII(OH), because odd-electron homolytic O-O bond cleavage is inhibited.

154 ylperoxo intermediate is proposed to undergo homolytic O-O bond cleavage to yield an oxoiron(IV) spec

155 res of Mn(III)-OOR decay are consistent with homolytic O-O bond scission.

156 onuclear LCu(II)(OOR) intermediate undergoes homolytic O-O cleavage to generate reactive RO(*) specie

157 roceeds via a direct 1,2-acyl migration, via homolytic O-O cleavage, or via a benzene oxide-oxepin re

158 oxidation and are assumed to react only via homolytic O-O dissociation in existing kinetic models.

159 s the heterolytic cleavage and gives rise to homolytic O-OH cleavage, and (b) the Thr302/water cluste

160 The unprecedented homolytic opening of ozonides promoted and catalyzed by

161 Elimination could be initiated either by homolytic or by heterolytic cleavage of this bond.

162 lorobenzoyloxy group apparently derived from homolytic oxygen-oxygen bond cleavage.

163 Rather a homolytic P-C bond cleavage in the labile aryl phosphine

164 d radical-trap studies are consistent with a homolytic pathway for C-X bond cleavage.

165 the allene oxide formed by selection of the homolytic pathway normally, while it inactivates by the

166 the occurrence of either a heterolytic or a homolytic pathway results from their competition as a fu

167 is crucial for the formation of Cpd I in the homolytic pathway.

168 ght; was faster than would be expected for a homolytic process given known Co-C bond dissociation ene

169 ol leads to products by both heterolytic and homolytic processes.

170 echanism of H2 over ceria, leading to either homolytic products (surface OHs) on a close-to-stoichiom

171 riguing to find that mutases, which catalyze homolytic rather than heterolytic cleavage of the carbon

172 ted with the two pathways indicates that the homolytic reaction (Co(III)H + Co(III)H --> 2 Co(II) + H

173 e enthalpy and entropy of activation for the homolytic reaction (deltaH = -1.2 kcalmol and deltaS= -3

174 the following activation parameters for the homolytic reaction at 37 degrees C: DeltaH(f)() = 18.8 +

175 propose a modified mechanism that involves a homolytic reaction of the olefin with a copper(II)-activ

176 d the gas phase occurred exclusively through homolytic reactions, while in methanol, they occurred pr

177 However, although rare, radical (homolytic) reactions are much more common than electroph

178 paths and propose a mechanism involving the homolytic reductive elimination of hydrogen.

179 n mechanisms, the VC and EC moieties undergo homolytic ring opening from their respective reduction i

180 hydrogen by two competing pathways: a slower homolytic route involving two Co(III)-H species and a do

181 ain conformational change to orchestrate the homolytic rupture of the Co-C bond.

182 es not impact significantly on the Co-C bond homolytic rupture, rendering it unusually stable, and th

183 o 31 for pK(a) values, 43 to 68 kcal/mol for homolytic SBDFEs, and 44 to 84 kcal/mol for hydride dono

184 deoxyadenosyl radical through enzyme-induced homolytic scission of the Co-C bond.

185 ion of O-sialyl hydroxylamines by reversible homolytic scission of the glycosidic bond following the

186 cals with heme iron (Fe(III)), followed by a homolytic scission of the N-O bond and transfer of the n

187 tional modes by tunneling electrons leads to homolytic Si-Si bond rupture.

188 de electrochemical potentials, pK(a) values, homolytic solution bond dissociation free energies (SBDF

189 For comparison, the calculated homolytic strength of the N--NO bond is 40.0 kcal/mol (M

190 is forced to take an alternative route: the homolytic substitution (S(H)2) of the sulfide sulfur by

191 re thought to occur by concerted bimolecular homolytic substitution (S(H)2), and the third one, *CN t

192 suggesting the possibility of intramolecular homolytic substitution at sulfonyl sulfur may be explain

193 On this basis, it is concluded that homolytic substitution at sulfonyl sulfur, if possible a

194 oposed to proceed via a stepwise associative homolytic substitution at the Pd center of 1 with format

195 strate that propargyl radicals could undergo homolytic substitution at zinc.

196 t to proceed through radical chains in which homolytic substitution of a disulfide by an NHC-boryl ra

197 allyl and pentadienyl peroxyl radicals, and homolytic substitution of carbon radicals on the peroxid

198 However, their reactivity in homolytic substitution processes is strongly reduced whe

199 ction thermochemistry prove that bimolecular homolytic substitution, S(H)2, of the acetamide radical

200 pport that, in the case of iodo derivatives, homolytic thienyl-I bond fragmentation occurs first and

201 of cobalamin influences both the mode (i.e., homolytic vs heterolytic) and the rate of Co-C bond clea

202 Homolytic W-H bond dissociation free energies are 59.3(3

203 the hydrogen-atom donors, but not the lowest homolytic X-H (X = heavy atom) bond dissociation energie