ライフサイエンスコーパス: homolysis

1 ex, which is therefore nicely set up for O-O homolysis.

2 ich to investigate the mechanism of coenzyme homolysis.

3 , for example, through visible-light-induced homolysis.

4 to generate a glycosyl radical via C-O bond homolysis.

5 Furthermore, Int II is formed by N-O bond homolysis.

6 luminate the mechanism of excited-state bond homolysis.

7 fluoroacetate (TFA) by visible light-induced homolysis.

8 radical generation, presumably via Fe-C bond homolysis.

9 y light-induced, excited-state Ni(II)-C bond homolysis.

10 derivative that was unstable toward Fe-CH(3) homolysis.

11 tive complexation-induced carbon-carbon bond homolysis.

12 used to effect reversible carbon-carbon bond homolysis.

13 gers (TEMPO, benzophenone) induce Al-Fe bond homolysis.

14 ode that is consistent with both C-H and O-H homolysis.

15 bon-carbon activation and carbon-oxygen bond homolysis.

16 nd a crossing to the LS surface for O-O bond homolysis.

17 through chain-walking followed by Ni-C bond homolysis.

18 isms by which the Co-C bond is activated for homolysis.

19 O-phenyloximes produces 1-tetralones via N-O homolysis, 1,5-hydrogen atom transfer (HAT), and cycliza

20 The synthesis by Ln(III)-A homolysis allows [5f(1)-4f(n)]2 and Li[5f(1)-4f(n)] comp

21 e irradiation of O-phenyloximes triggers N-O homolysis and 1,5-hydrogen atom transfer (HAT), resultin

22 adiation of 9 led principally via SO2-N bond homolysis and [1,5] sigmatropic rearrangement to generat

23 Ph, it was shown that C-O cleavage occurs by homolysis and by 1,2-elimination in a ratio of 1.4:1, re

24 ls and differences in mechanisms of O-O bond homolysis and electrophilic H-atom abstraction reactions

25 e of substrate, catalyzes carbon-cobalt bond homolysis and formation of a thiyl radical from an activ

26 denitroxylation) of the nitrite via O-N bond homolysis and H-abstraction from the resultant benzyloxy

27 We conclude that homolysis and heterolysis of the dioxygen bond with form

28 H bond, of which the most widespread are M-H homolysis and R-H reductive elimination.

29 etric geminate recasting: a process in which homolysis and recombination occur within a solvent cage

30 ersible photoswitching process, in which the homolysis and reformation of carbon-carbon single bonds

31 stribution of prototropic isomers in driving homolysis and stabilizing radical intermediate states is

32 ond followed by a Rh(III)-triggered N-S bond homolysis and sulfonyl radical migration.

33 nal aldimine and elicit the AdoCbl Co-C bond homolysis and the accumulations of cob(II)alamin and ana

34 2-thiolglutarate elicits cobalt-carbon bond homolysis and the formation of 5'-deoxyadenosine.

35 spect to wt-RTPR-mediated carbon cobalt bond homolysis and the intermediacy of the 5'-deoxyadenosyl r

36 hich Omega liberates 5'-dAdo* by Fe-C5' bond homolysis, and the 5'-dAdo* attacks the dehydroalanine r

37 subdivide by the functional group undergoing homolysis, and thereafter by the type of transformation

38 he enzyme-bound state, the RP generated upon homolysis appears to be stabilized against the extent of

39 generated via photoinduced Ni-C(sp(2)) bond homolysis are involved in hydrogen atom abstraction from

40 nvestigations unambiguously support O-O bond homolysis as the predominant pathway of heme-PN decay, l

41 nt effects point to heterolysis, rather than homolysis, as the step that breaks the S-O bond.

42 lallenes racemize by reversible thermal bond homolysis at 95 degrees C; racemization of these metalla

43 NON)Al-FeCp(CO)(2) (1), undergoes Al-Fe bond homolysis at ambient conditions to reveal the [(NON)Al](

44 lower the kinetic barrier to bimetallic O(2) homolysis at five-coordinate oxorhenium(V) by facilitati

45 ied before are much less suited for O-O bond homolysis, because the resulting Cu(III)=O species is le

46 Together, these results are consistent with homolysis becoming completely rate determining in the fo

47 rvation is consistent with adenosylcobalamin homolysis being slowed relative to hydrogen abstraction

48 H(3)SONO, readily releases NO on (S)O-N bond homolysis but CH(3)SONO formation from CH(3)SNO(2) eithe

49 CoA mutase accelerates the rate of Co-C bond homolysis by a factor of approximately 10(12).

50 ly that redox-active ligands facilitate O(2) homolysis by lowering the barrier to the formally spin-f

51 ransfer to the iron center subsequent to C-H homolysis competes with ring-opening in the processing o

52 those alkoxyamines that decompose by the N-O homolysis/disproportionation pathway are much less effec

53 mplementary TA actinometry indicate that the homolysis efficiency is limited by relaxation to a lower

54 adicals as transient activating groups, this homolysis-enabled electronic activation strategy provide

55 that correlates with (2)A(1) lowers the O-O homolysis energy by approximately 15 kcal/mol, similar t

56 ed mechanism hypothesized to involve a Ni-Br homolysis event from an excited-state nickel complex.

57 nsistent with an initial Norrish type I like homolysis followed by a radical mediated depropagation r

58 bstrates and diphenylamines decompose by N-O homolysis followed by disproportionation.

59 complex, Cr(aq)OONO(2+), undergoes O-O bond homolysis followed by some known and some novel chemistr

60 h a stepwise reaction mechanism via N-O bond homolysis following the second energy transfer event to

61 antification of the Mn-Cl bond dissociation (homolysis) free energy of 21 and 23 +/- 7 kcal/mol at ro

62 light to promote efficient Ni-C(sp(2)) bond homolysis from cationic Ni(III) and C(sp(2))-C(sp(3)) re

63 necessary for blue-light-triggered Pd-C bond homolysis from this alpha-carbon to form a carbon-center

64 BDFE = 44 kcal/mol) leads to bimetallic H-H homolysis, generating trans-Fe(II)(H)(H(2))(+).

65 f the Co-C bonds is much more favorable than homolysis (>21 kcal/mol) and is significantly more exerg

66 ddition, the reaction coordinate of the Fe-O homolysis has been investigated, which is a possible dec

67 of the sulfonamide linkage to excited-state homolysis holds comparative interest.

68 The C-ON bond homolysis in alkoxyamine 2a was chemically triggered by

69 The C-ON bond homolysis in alkoxyamines can be influenced by the prese

70 roxide played an important role in C-ON bond homolysis in alkoxyamines.

71 f the Fe-C5' bond, in analogy to Co-C5' bond homolysis in B(12), which was once viewed as biology's c

72 l as a powerful oxidant to initiate C-H bond homolysis in bound substrates.

73 ribute to the rate acceleration of Co-C bond homolysis in EAL.

74 to contact ion pairs following photoinduced homolysis in solution is studied using picosecond pump-p

75 hat the resulting Ni-C bond does not undergo homolysis in subsequent stages of the catalytic cycle.

76 l-oxo intermediate stability enables the O-O homolysis in the case of iron but directs the copper com

77 elerates O(2) binding and minimizes O-O bond homolysis in the reduction of H(2)O(2).

78 Direct measurements of the rate of Ti-O bond homolysis in Ti-TEMPO complexes Cp2TiCl(TEMPO) (3) and C

79 weak substrate X-H bonds via small molecule homolysis is a powerful strategy in synthesis and has be

80 These results suggest that Co-C bond homolysis is coupled to hydrogen atom abstraction from t

81 )](x)(+) and the reaction coordinate for O-O homolysis is explored for both the low-spin and the high

82 The O-O bond homolysis is found to be endothermic by only 15 to 20 kc

83 This implies a mechanism in which Co-C bond homolysis is kinetically coupled to substrate hydrogen a

84 ate that the energy of the Calpha Cbeta bond homolysis is predominantly affected by the stability of

85 study of catalytic carbon-carbon sigma-bond homolysis is presented.

86 th deuterated substrates; this suggests that homolysis is slowed relative to hydrogen abstraction by

87 suggest that self-discharge through solvent homolysis is the cause of the observed limitations.

88 vel ab initio calculations, we show that N-O homolysis is the most likely fragmentation pathway avail

89 ndicate that visible-light-induced Ti-C bond homolysis is the rate-determining step.

90 s generated through photochemical Ts-Br bond homolysis lead to the formation of cyclic dibromide side

91 ermolysis of the complex results in N-O bond homolysis, leading to the formation of an iron(III) oxo

92 alues of >8.5 in CH(3)CN results in O-O bond homolysis, leading to the formation of hydroxyl radicals

93 escape of the alkoxyl radicals following N-O homolysis leads to significantly less effective regenera

94 Significantly, this soft homolysis mechanism provides a method to generate closed

95 t with the calculations for the H-bonded O-O homolysis mechanism.

96 ers on oxidative N-H, O-H, S-H, and C-H bond homolysis methods, for the generation of the correspondi

97 oxyamines, in contrast to the more usual C-O homolysis observed for the closely related N-alkoxyamine

98 stopped-flow kinetic measurements of AdoCbl homolysis obtained with deuterated substrates.

99 ning is a phenomenon wherein ligand X-H bond homolysis occurs in concert with the energetically favor

100 yl radical clock, demonstrate that Fe-C bond homolysis occurs reversibly.

101 of fac-[Re(dmb)(CO)(3)(CH(3)CN)]PF(6) or by homolysis of [Re(dmb)(CO)(3)](2).

102 sulfinyl radical (X-Cys SO .-Y) ions through homolysis of a Calpha Cbeta bond.

103 II)(A)3 (A = N(SiMe3)2, OC6H3Bu(t)2-2,6) via homolysis of a Ln-A bond.

104 nism involving decarbonylation and Ni-C bond homolysis of a Ni(II) adduct is proposed.

105 eCN)(n) Ni(III) (C(2) F(5) )(3) ], reductive homolysis of a perfluoroethyl radical occurs, with the c

106 ological redox processes, enables the formal homolysis of a stronger amide N-H bond in the presence o

107 the N-tosyl moiety by visible light-induced homolysis of a transient Cu(II)-tosylamide complex is pr

108 r 4, consistent with a process involving the homolysis of a weak Ti-O bond to generate the transient

109 on the ability of the enzyme to catalyze the homolysis of adenosylcobalamin has been investigated usi

110 yleneglutarate to glutamate mutase initiates homolysis of adenosylcobalamin.

111 s revealed that L-2-hydroxyglutarate-induced homolysis of AdoCbl occurs very rapidly, with a rate con

112 t k(d) of the chemically activated C-ON bond homolysis of alkoxyamines was subject to solvent effects

113 products arises predominantly from C-N bond homolysis of an intermediate ammonium ylide, followed by

114 to known systems are consistent with initial homolysis of an Ir-H bond being rate-determining.

115 major photoproduct channels corresponding to homolysis of aryl-OO and arylO-O bonds resulting in loss

116 Bi(I) catalyst, followed by a light-induced homolysis of Bi(III)-O bond to generate a trifluoromethy

117 Further, the aryl radical formed by the homolysis of C-X bonds in this technique was captured fo

118 Homolysis of C1-C8 to give a conformationally flexible d

119 uggested the generation of CO(2)(*-) through homolysis of cesium formate in the presence of light, an

120 The O-O bond homolysis of cis,cis-ONOONO is particularly interesting

121 presence of substrate, the rate of Co-C bond homolysis of enzyme-bound AdoCbl is increased by 12 orde

122 Our findings demonstrate that reversible homolysis of even weak M-C bonds is a feasible protectiv

123 aks down to release NO more readily than via homolysis of GSNO.

124 The homolysis of I(O) is much favored over that of the neutr

125 mol) in the rate-determining step, i.e., the homolysis of I2k, agreed well with the experimental valu

126 the spin state changes to triplet during the homolysis of I2k; in this way two malonyl radicals are f

127 d to achieve efficient visible-light induced homolysis of iron azide species and the cooperation with

128 and introduce SO(4)(-*), generated by 248 nm homolysis of low millimolar levels of persulfate, as a r

129 The homolysis of O-O bond produces NO(2) and L(2)(H(2)O)RhO(

130 t takes place downstream to the EnT-mediated homolysis of our reagent(s).

131 -migration mechanism of deamination-and that homolysis of SAM concomitant with H atom abstraction fro

132 -adenosylmethionine (SAM) enzyme, catalyzing homolysis of SAM to 5'-deoxyadenosine (5'-dAdo) in the p

133 from water (H(2)O) can effectively drive the homolysis of strong C(sp(3))-Si bonds, enabling radical

134 -2,4-diaminobutryic acid (DAB) induces rapid homolysis of the AdoCbl Co-C bond (781 s(-1), D-ornithin

135 orresponding imidazolium salts mainly caused homolysis of the ArO-S bond.

136 generation of a phenoxyl radical via formal homolysis of the aryl O-H bond enables direct nucleophil

137 Methoxy substituents enhance the homolysis of the beta-O-4 linkage, relative to PPE, in o

138 i(I) complex to CH(2)I(2), (2) light-induced homolysis of the Bi(III)-CH(2)I bond, (3) subsequent iod

139 s support a radical relay pathway: oxidative homolysis of the C-B bond generates prochiral alkyl radi

140 nzo[ghi]fluoranthene as the major product by homolysis of the C-Cl bond, 1,4-shift of a hydrogen atom

141 alkyl fragment was suitable to activate the homolysis of the C-ON bond.

142 lent Ni(I) state, lights the fuse leading to homolysis of the C-S bond of methyl-coenzyme M (methyl-S

143 By exploiting phosphine-induced homolysis of the C-Se and C-S bonds of selenocysteine an

144 his exchange reaction in which RNR catalyzes homolysis of the carbon-cobalt bond in a concerted fashi

145 B12-dependent reactions, is postulated to be homolysis of the Co-C bond of the cofactor.

146 rate that the enzyme accelerates the rate of homolysis of the cobalt-carbon bond by at least 10(12)-f

147 ing further support for a mechanism in which homolysis of the coenzyme is coupled to hydrogen abstrac

148 It was found that homolysis of the coenzyme is slower by an order of magni

149 pparent rate constants for substrate-induced homolysis of the coenzyme that are slower by 7-fold and

150 terium isotope effects that are observed for homolysis of the coenzyme when the wild-type enzyme is r

151 y use substrate binding energy to accelerate homolysis of the coenzyme.

152 )(CO)2Os(*) radicals, formed by photoinduced homolysis of the corresponding osmium dimers.

153 he catalytically active intermediate through homolysis of the Fe-C5' bond, in analogy to Co-C5' bond

154 IX2 (X = (pseudo)halide), that undergo rapid homolysis of the hypervalent I-X bonds and generate (pse

155 m that the rearrangement is triggered by the homolysis of the isoxazolidine N-O bond followed by clea

156 oducts (ca. 20 mol %) are also formed by C-O homolysis of the methoxy group.

157 First, homolysis of the N-OH bond in 2 may yield the well-known

158 which undergoes facile fragmentation through homolysis of the N-R bond.

159 In organic solvents, light-induced homolysis of the N-S bond occurs, and the resulting aryl

160 t-lived singlet excited state that undergoes homolysis of the Ni-H bond.

161 t-initiated triplet energy transfer promotes homolysis of the O-O bond in di-tert-butyl or dicumyl pe

162 eroxyhemiacetal intermediate promotes facile homolysis of the O-O bond.

163 Instead, homolysis of the Omega Fe-C5' bond generates the nominal

164 s by ONOOH and NO(2)(*), a radical formed by homolysis of the ONOOH bond, is unusually rapid but that

165 However, proton-assisted homolysis of the peroxo hemiacetal intermediate to produ

166 IV) (O) and (.) NO2 species through O-O bond homolysis of the peroxynitrite ligand.

167 from the OOH to the OH ligand and the other homolysis of the Pt-OOH bond, abstraction of the OH liga

168 tion of a cyclic amine, followed by N-I bond homolysis of the resulting intermediate and subsequent a

169 attack by the amine on the peroxide but that homolysis of the resulting intermediate is the rate-dete

170 ficantly faster than can be accounted for by homolysis of the S-N bond.

171 xygenation of the oxoammonium cation through homolysis of the weak N-O bond, differing from prototypi

172 y EPR spectroscopy that they underwent clean homolysis of their N-O bonds upon UV photolysis.

173 glycerol but have not done so in the thermal homolysis of this bond in the enzyme-bound cofactor in t

174 of reductively generated Co(II)H rather than homolysis of two Co(III)H units.

175 imerization, with visible-light-induced bond homolysis offers a new entry point into catalytic alkyne

176 Thus, photoinduced Ni-aryl homolysis offers a novel mechanism of initiating catalys

177 xcited states that lead to metal-ligand bond homolysis on the subnanosecond time scale to access synt

178 tion from CH(3)SNO(2) either by S-NO(2) bond homolysis or concerted rearrangement faces prohibitively

179 oxidizing radicals derived from its O-O bond homolysis, or the other oxidants under study.

180 complexes, which exclusively undergo a Cu-C homolysis pathway to generate alkyl radicals and Cu(II)

181 Surprisingly, molecule-assisted homolysis plays a key role in this transformation, the d

182 ng alphabeta absorption band results in bond homolysis proceeding via a bound cob(III)alamin MLCT sta

183 tonic energy and leverage excited-state bond homolysis processes in synthetic chemistry.

184 served in the spectroscopic data of the post-homolysis product Co2+ Cbl when bound to glutamate mutas

185 of the reduced B12 cofactor (i.e., the post-homolysis product Co2+ Cbl) is modulated by the enzyme m

186 ctivation involves stabilization of the post-homolysis product, Co2+ Cbl, rather than destabilization

187 O2Me)FeIII(OH) give both O-O heterolysis and homolysis products, Compound I (Cpd I) and Compound II (

188 iven the extremely fast back-reaction of the homolysis products, heterolysis probably dominates the o

189 gh enzyme-mediated stabilization of the post-homolysis products.

190 ugh stabilization of the Co(2+)Cbl/Ado. post-homolysis products.

191 The motivation to develop amide homolysis protocols stems from the utility of the result

192 via thermal or photochemical M-C sigma-bond homolysis, radical formation is triggered solely by coor

193 ion of two kinetic parameters, the C-ON bond homolysis rate constant (kd) and its re-formation rate c

194 up (OMe, OAc, OBz, OBn, or OTBDMS), a higher homolysis rate constant k(d) is observed, as expected fr

195 ts, which leads to an 8-fold decrease in the homolysis rate constant k(d).

196 given excitation wavelengths, photochemical homolysis rate constants span 2 orders of magnitude acro

197 Comparison of the homolysis rate for the free and enzyme-bound cofactors r

198 trillion-fold acceleration of Co-carbon bond homolysis rate in the methylmalonyl-CoA mutase-catalyzed

199 ctrophotometry, we demonstrate that the Co-C homolysis rate in the presence of protiated substrate ha

200 ecreases their energies and enhances the O-O homolysis rate, which is consistent with the acceleratio

201 thermodynamic parameters associated with the homolysis reaction catalyzed by methylmalonyl-CoA mutase

202 ATR induces a sacrificial cobalt-carbon bond homolysis reaction in an unusual reversal of the heterol

203 The homolysis reaction of the HS [(TMC)Fe(III)-OOH](2+) comp

204 t could not be directly determined including homolysis reactions of the Rh(II)-Rh(II) dimer with wate

205 ence of CO(2), and also in the types of bond homolysis reactions that PNA and PNI may undergo.

206 proton-controlled, 2e- (heterolysis) vs 1e- (homolysis) redox specificity sheds light on the exceptio

207 )Pr2)3Co-N2 (5) via a proposed Co-alkyl bond homolysis route.

208 ad end" since the radical pairs generated by homolysis should mostly revert to starting material.

209 all the enzymes that have been examined, the homolysis step is kinetically indistinguishable from abs

210 also results in isotope effects on coenzyme homolysis that are much smaller than the very large effe

211 Both complexes undergo visible-light-induced homolysis that is significant to their activity but exhi

212 Leveraging photoinduced metal-ligand bond homolysis, these PCs generate reactive intermediates ran

213 S of 96 cal mol-1 K-1 for carbon-cobalt bond homolysis/thiyl radical formation.

214 nds locks the HO. radical, formed by the O-O homolysis, thus directing it to exclusively abstract the

215 e-steady-state kinetics of adenosylcobalamin homolysis to be investigated by stopped-flow spectroscop

216 ce of weak C-H bonds, but decay via N-O bond homolysis to ferrous or ferric iron hydroxides in the pr

217 I(O) undergoes O-O homolysis to form a biradical Bt, which is fragmented in

218 ydrofuran as solvent, the O-O bond undergoes homolysis to generate (*)NO2 (detected spectrophotometri

219 OONO) coordination, which undergoes O-O bond homolysis to generate a putative cupryl (LCu(II) -O(.) )

220 the excited Ni(II) complexes can undergo Ni homolysis to generate aryl radicals and Ni(I), both of w

221 al cation, [CpW(CO)(2)(IMes)H](*+), W-H bond homolysis to generate the 16-electron cation [CpW(CO)(2)

222 plex in photoinduced LMCT and its subsequent homolysis to generate the alkyl radial through the exclu

223 rrangement involves excited state ArO-C bond homolysis to give para-substituted phenoxyl radicals, wh

224 (and [Cu(I)(Me(6)tren)](+)) by Cu(II)-O bond homolysis to promote efficient eATRA.

225 (3)-azidoiodane reagent to undergo I-N bond homolysis under mild conditions to form (2)-iodanyl and

226 The weak O-N bond of 3a is susceptible to homolysis under photolysis conditions, and the radical 7

227 he same ligand framework undergoes Pd-C bond homolysis under visible light irradiation to form the sa

228 t is presented, which may undergo sigma-bond homolysis upon visible-light-induced sensitization to fo

229 The experimentally validated B-Cl bond homolysis was synthetically exploited for a BCl(3)-media

230 nostic agents by activation of the C-ON bond homolysis, we turned our interest to the chemical activa

231 [Fe(4)S(4)]-alkyl clusters undergo Fe-C bond homolysis when the alkylated Fe site has a suitable coor

232 d before the barrier; the other involves O-O homolysis, where the phenol remains H-bonding to the per

233 keto-enol tautomerism is feasible, enol N-O homolysis, which forms the more stable acetic acid radic

234 report the first light-induced Pd(IV)-C bond homolysis, which leads to the formation of alkyl radical

235 The rate of Co-C bond homolysis, while slow for the free cofactor, is accelera