ライフサイエンスコーパス: aldimine

1 complexes, cysteinyl aldimine and glutaminyl aldimine.

2 s-313 to generate the product-bound external aldimine.

3 og trapped in the active site as an external aldimine.

4 tures of the ASL complexes with the internal aldimine.

5 ity that is not associated with the internal aldimine.

6 e-258 than the deprotonation of the external aldimine.

7 han preservation of the fate of the external aldimine.

8 crylate without accumulation of the external aldimine.

9 ovided by the lysine that forms the internal aldimine.

10 f the glycine pro-R proton from the external aldimine.

11 nting the formation of the L-serine external aldimine.

12 mined spectrophotometric pKa of the internal aldimine.

13 ximately 20 degrees relative to the internal aldimine.

14 ate results in the formation of the external aldimine.

15 nal aldimine with the PLP-substrate external aldimine.

16 0.6 +/- 3.8 s(-1) and re-formed the internal aldimine.

17 reaction after the formation of the external aldimine.

18 use of o-thiomethyl-p-methoxyaniline-derived aldimines.

19 nation precatalyst of diphenylacetylene with aldimines.

20 broad substrate range including nonaromatic aldimines.

21 hons for enantioselective additions to N-Boc-aldimines.

22 ative to the classical methods for preparing aldimines.

23 e reactions, especially for the synthesis of aldimines.

24 nozinc reagents to a variety of alpha-chloro aldimines.

25 racemic donor-acceptor cyclopropanes and (E)-aldimines.

26 d aryl organometallic reagents to N-sulfinyl aldimines 1 and 2 and ketimines 5 and 6.

27 wide range of N-p-(methoxy)phenyl protected aldimines 3 derived from alkyl, aryl, and heteroaryl ald

28 tepwise reaction by formation of an external aldimine adduct with the PLP cofactor.

29 uent radical-radical coupling with secondary aldimines affords a variety of beta-amino ether products

30 ated between the alpha-site and the external aldimine, alpha-aminoacrylate, and quinonoid forms of th

31 favors this form in its equilibrium with Ala aldimine and Ala ketimine.

32 bind to the allosteric site in the internal aldimine and alpha-aminoacrylate external aldimine forms

33 the rates of the interconversion of external aldimine and aminoacrylate intermediates in the Tryptoph

34 sition state for interconversion of external aldimine and aminoacrylate intermediates in the Tryptoph

35 and approximately 340 nm, is assigned as Cys aldimine and Cys ketimine forms in rapid equilibrium.

36 DAB, and 2,3-DAPr bind to PLP as an external aldimine and elicit the AdoCbl Co-C bond homolysis and t

37 rming external aldimine complexes, cysteinyl aldimine and glutaminyl aldimine.

38 te interconversion at the stages of external aldimine and ketimine formation.

39 enzyme and for the stability of the external aldimine and ketimine intermediates.

40 Under similar conditions, aldimine and ketimine produced oxaziridines.

41 ed for Schiff base formation in the internal aldimine and later as a general base.

42 give, as in solution, a mixture of external aldimine and quinonoid intermediates and gem-diamine and

43 l-Met and l-Phe to form mixtures of external aldimine and quinonoid intermediates as in solution.

44 s to form equilibrating mixtures of external aldimine and quinonoid intermediates in rapid-scanning s

45 c evidence for the formation of the external aldimine and quinonoid intermediates in the reactions of

46 rosine form equilibrium mixtures of external aldimine and quinonoid intermediates when they bind to T

47 e to form equilibrating mixtures of external aldimine and quinonoid intermediates, absorbing at appro

48 s to form equilibrating mixtures of external aldimine and quinonoid intermediates, similar to those o

49 , to form equilibrating mixtures of external aldimine and quinonoid intermediates.

50 ) gives an equilibrating mixture of external aldimine and quinonoid species, E(Aex)(his) and E(Q)(his

51 x with PMP alone as well as the PLP internal aldimine and show that the dimeric structure of WbpE obs

52 ligned with the p orbitals of the conjugated aldimine and thus maximizes stereoelectronic effects.

53 ned to the endocyclic proton of the internal aldimine and to the bridging hydrogen bond, respectively

54 cycloaddition reaction between N-(3-pyridyl)aldimines and acetylenes where 1,5-naphthyridines are ob

55 d, starting from N-protected trifluoromethyl aldimines and cyclic or acyclic beta-keto esters bearing

56 h formal [2 + 2] cycloadditions with N-tosyl aldimines and formal [4 + 2] cycloadditions with either

57 ant, suggested rapid equilibrium of isomeric aldimines and geminal diamines.

58 ve for amine dehydrogenation to give N-alkyl aldimines and H(2).

59 tert-Butanesulfinyl aldimines and ketimines bearing an alpha-benzyloxy or al

60 s been designed and synthesized; its derived aldimines and ketimines have been applied for asymmetric

61 amides provide stable bicyclic and tricyclic aldimines and ketimines in good yields.

62 reaction of substituted donors with N-tosyl aldimines and ketimines in high regio-, diastereo-, and

63 Pr)(3) ester enolates to tert-butanesulfinyl aldimines and ketimines provided beta-substituted, alpha

64 alkynes and alpha,beta-unsaturated N-benzyl aldimines and ketimines that proceeds through dihydropyr

65 gh diastereoselectivity to chiral N-sulfinyl aldimines and ketimines to provide alpha-amino amides.

66 for aromatic, heteroaromatic, and aliphatic aldimines and ketimines using ethyl cyanoformate as the

67 ntioselective for the addition of cyanide to aldimines and ketimines.

68 to be effective in addition to both N-tosyl aldimines and N-tolyl sulfinimines, the latter reaction

69 elective addition of alkylazaarenes to N-Boc aldimines and nitroalkenes under mild conditions.

70 PLP is covalently bound via an internal aldimine, and residues from both domains and both subuni

71 e Grignard addition to a tert-butanesulfinyl aldimine, and ring closing olefin metathesis as key step

72 Furthermore, this aldimine appears to be inappropriately aligned for effic

73 Aziridination of N-tosyl aldimines applying modified hydroxylamine under asymmetr

74 nserved, yet the pK(a)'s of the two internal aldimines are 9.3 and 7.0, respectively, to complement t

75 n of a broad range of carbonyl compounds and aldimines are disclosed.

76 A variety of aryl and aliphatic N-Boc-aldimines are effective substrates for this transformati

77 Catalytic allylboron additions to aldimines are presented for which small amounts of Zn(OM

78 esonance-stabilized structure of the PLP-Ser aldimine as seen in aminotransferases.

79 to the unprotonated tautomer of the external aldimine as well as the appearance of a new fluorescent

80 a broad range of trifluoromethyl imines and aldimines as nucleophiles to engage in chemo-, regio-, d

81 product UDP-GlcNAc(3NH(2))A as the external aldimine at 1.9 A resolution.

82 also be used for catalytic hydrogenation of aldimines at room temperature via a frustrated Lewis pai

83 els-Alder reactions of the alkyl-substituted aldimines bearing the structurally modified N-aryl unit

84 Four prototropic isomers of a model aldimine between AIB and 5'-deoxypyridoxal, with acetate

85 In the resting enzyme, an internal aldimine between PLP and an essential lysine in the acti

86 The internal aldimine between pyridoxal 5'-phosphate and the epsilon-

87 Since the internal aldimine bond between the protein lysine, Lys33, and C4'

88 alently bound to the protein via an internal aldimine bond with Lys42.

89 system between the PLP ring and the internal aldimine bond.

90 on with ethylenediamine and reduction of the aldimine bonds formed.

91 are strengthened in the presence of external aldimines bound to the beta-site.

92 th PLP, shows slow formation of the external aldimine but does not form the alpha-aminoacrylate inter

93 ample, from additions to protected/activated aldimines), but those involving ketimines are much less

94 erates both tautomeric forms of the external aldimine, but with D-ornithine the equilibrium is shifte

95 gests that the chemical fate of the external aldimine can be redirected by modifications at the N-ter

96 ive Mannich-type reaction of azlactones with aldimines catalyzed by a chiral phosphoric acid is descr

97 lts, which possibly stabilize the protonated aldimine coenzyme complex.

98 on of the Tryptophan synthase L-Ser external aldimine complex at 495 nm, with 420 nm excitation, prov

99 with the substrate, and its product external aldimine complex have been determined at 1.46, 1.8, and

100 for the adsorption complex and the external aldimine complex of the enzyme with the substrate.

101 by motion of the l-Trp indole moiety of the aldimine complex, contributes to quinonoid intermediate

102 Crystal structures of the internal aldimine complexed with G3P and with three of the new AS

103 with cysteine or glutamine forming external aldimine complexes, cysteinyl aldimine and glutaminyl al

104 ria between different quinonoid and external aldimine complexes.

105 le previously reported internal and external aldimine complexes.

106 The synthesis features the use of an enolate-aldimine condensation between a chiral glycine aluminum

107 Cyclization of aromatic ketimines and aldimines containing alkenyl groups tethered at the meta

108 ene to alpha-ketoesters or N-benzenesulfonyl aldimines corroborate a catalytic mechanism involving C

109 Aldimine coupling (AIC) is the nitrogen analogue of the

110 Cyanide-catalyzed aldimine coupling was employed to synthesize compounds w

111 ydroxylation was shown to alter the divalent aldimine cross-link chemistry of mutant skin collagen.

112 uman breast cancer cells were embedded in 3D aldimine cross-linked collagen matrices and used as an i

113 equent reaction with hydrogen-bond-activated aldimines delivers beta-aminocarbonyl compounds with hig

114 mbination of these effects leads to a stable aldimine derivative and potent inactivation of alanine r

115 reacted with optically pure trifluoromethyl aldimine derived from (R)-alpha-methylbenzylamine, givin

116 a wide range of N-p-methoxyphenyl-protected aldimines, derived from alkyl, aryl and heteroaryl aldeh

117 As expected, BAPN inhibited the formation of aldimine-derived cross-links in collagen, and the constr

118 Borohydride reduction of the native enzymic aldimines did not increase the denaturation temperature

119 ) chloride and sulfate increase the external aldimine dissociation constants for O-acetyl-L-serine, L

120 t, formation of the L-Ser and L-Trp external aldimines E(Aex1) and E(Aex2) at the beta-site causes a

121 ), which converts to the alpha-aminoacrylate aldimine, E(A-A).

122 nts for the conversion of the L-Ser external aldimine, E(Aex1), to E(A-A) show that the primary kinet

123 In stage I, l-Ser forms an external aldimine, E(Aex1), which converts to the alpha-aminoacry

124 be the allosteric properties of the internal aldimine, E(Ain).

125 (gamma-thialysine) or external (ethylamine) aldimine followed by the slow formation of the alpha-ami

126 mplex and the pyridoxal 5'-phosphate-glycine aldimine, followed by the abstraction of the glycine pro

127 posits two parallel pathways to the external aldimine for this mutant, the minor one has the alpha-am

128 brium isotope effect ((2)H-EIE) favoring the aldimine form (417 nm) is observed in the second state p

129 structure of NtdA alone reveals the internal aldimine form of NtdA with the cofactor pyridoxal phosph

130 udies of the ASL complexes with the internal aldimine form of the enzyme establish the following.

131 ydryl group of the substrate on the internal aldimine form of the pyridoxal 5'-phosphate (PLP) cofact

132 sopropylamine, and glycine all have external aldimine formation as the rapid observable step, based o

133 ocyclohexane-1-carboxylate may have external aldimine formation as the rate-determining step.

134 rientation of the PLP cofactor upon external aldimine formation is impeded in H282A.

135 l-2-aminomalonate, indicating rapid external aldimine formation on this longer time scale.

136 anism (observed as a lag in the ALA external aldimine formation progress curve), consistent with conf

137 isotope effects were found for the external aldimine formation steps in both the L --> D (1.13 +/- 0

138 The spectral data indicate that external aldimine formation with either AIB or L-alanine and DGD-

139 the progress curve for the L-serine external aldimine formation, indicating a hysteretic behavior in

140 ted in the T148A-catalyzed L-serine external aldimine formation.

141 We show here that the external aldimine formed between PLP and GABA is apparently respo

142 arrangement mechanism, in which the external aldimine formed between PLP and lysine is initially conv

143 um changes characteristic of reduction of an aldimine formed between PLP and lysine.

144 situ generation and trapping of the reactive aldimine formed from urea and aldehyde by the diene syst

145 pH titration of the external aldimine formed with ALA indicated the D279E mutation in

146 In the second monomer, the external aldimine formed with the substrate analog.

147 NMR experiments on isotopically labeled PLP aldimines formed by lyophilization with poly-L-lysine.

148 The external aldimines formed upon addition of L-Ala or L-Ser are sta

149 al aldimine and alpha-aminoacrylate external aldimine forms of OASS; (iv) sulfate also binds to the a

150 cient biomimetic method for the synthesis of aldimines from aldehydes and compounds bearing the NH2 g

151 range of heteroaromatic and simple aliphatic aldimines gave anti-rich (approximately 3-19:1) beta-nit

152 (dimethylamino)vinyl]-1,3-dimethyluracil and aldimines has been developed for the construction of dih

153 xal 5'-phosphate (PLP) linked as an internal aldimine in alanine racemase (AlaR), aspartate aminotran

154 orption and emission spectra of the internal aldimine in the absence and presence of the product acet

155 The holo-SDH contained PLP-OMS aldimine in the active site, indicating that OMS can for

156 methionine covalently linked as an external aldimine in the active site.

157 n of the roles of aryl nitromethane and aryl aldimine in the key step, which revealed unique substrat

158 hile it is more similar to the open external aldimine in the presence of NH4(+).

159 ormation of the geminal diamine and external aldimine in this pathway were determined to be 25 and 4

160 adical rearrangement by forming a lysine-PLP aldimine, in which the imine group participates in the i

161 Mannich (VM) reactions of alkyl-substituted aldimines (including those bearing heteroatom-containing

162 formation (386 s-1 at 0.1 M) of an external aldimine intermediate absorbing at 420 nm, followed by s

163 e aminotransferase to give a stable external aldimine intermediate are reported.

164 e, and decanoyl-CoA shows a trapped external aldimine intermediate, suggesting that the condensation

165 ic orientation about C alpha in the external aldimine intermediate.

166 demonstrates that formation of the external aldimine intermediates and abstraction of the C alpha pr

167 rt a stepwise racemization of stereoisomeric aldimine intermediates in which a substrate-based carban

168 ble that stereoisomerization of the external aldimine intermediates occurs through a concerted double

169 in of V241 facilitates formation of external aldimine intermediates with primary amine substrates, wh

170 d intermediates and gem-diamine and external aldimine intermediates, respectively.

171 h accelerates the conversion of the external aldimine into the initial quinonoid intermediate.

172 e binding of L-allothreonine as the external aldimine is faster than formation of the 3-methyl aminoa

173 d by a slower reaction in which the internal aldimine is protonated on the Schiff base N.

174 bsorption spectra indicate that the external aldimine is the predominant L-serine intermediate and th

175 antioselective addition of an allene unit to aldimines is disclosed.

176 lkylation of indole and its derivatives with aldimines is efficiently catalyzed by a zinc-ProPhenol d

177 od for the enantioselective cinnamylation of aldimines is reported.

178 ogue onto PLP (i.e. formation of an external aldimine) is also rapid (532 s(-1), D-ornithine; 488 s(-

179 We infer that these represent the internal aldimine (lambda(max) 416 nm; A), two different unligand

180 a(max) at 409 nm; B and C), and the external aldimine (lambda(max) 426 nm; D).

181 the substrate Calpha-H bond in the external aldimine lies between those of the two catalytic bases,

182 The PLP forms an internal aldimine link to the Rossmann domain through Lys(629), e

183 The data indicate that the formation of the aldimine linkage between lysine 346 and PLP is important

184 his is characteristic of the reduction of an aldimine linkage between the carbonyl group of PLP and t

185 scopy with HemA suggested the presence of an aldimine linkage between the enzyme and pyridoxal 5'-pho

186 n a pyridoxal 5'-phosphate (PLP) molecule in aldimine linkage to Lys39 as a protonated Schiff base, a

187 /beta barrel and is covalently linked via an aldimine linkage to Lys39, which is at the C-terminus of

188 radical rearrangement by forming an external aldimine linkage with the epsilon-amino group of a subst

189 ex with the reduced analogue of the external aldimine, N-(5'-phosphopyridoxyl)-d-alanine (PPDA).

190 the phenolic oxygen (enolimine form) to the aldimine nitrogen (ketoenamine form) is often considered

191 7.7) from a form with a protonated internal aldimine nitrogen (lambdamax = 416 nm) to a deprotonated

192 phosphate, reducing the pKa of the internal aldimine nitrogen and promoting formation of quinonoid i

193 trols kcat/KAIB, is not deprotonation of the aldimine nitrogen.

194 l-depleted enzyme, formation of the external aldimine occurs over long time scales (approximately 50

195 ional change induced by the formation of the aldimine of 4-aminocyclopentane-1,3-dicarboxylic acid an

196 mM) decrease the proportion of the external aldimine of aminoacrylate and induce formation of the qu

197 We find that the gem-diamine and external aldimine of aminoacrylate are the primary intermediates

198 reaction with L-serine and that the external aldimine of aminoacrylate or its complex with L-homocyst

199 n the absence of L-homocysteine produced the aldimine of aminoacrylate, which absorbed at 460 nm and

200 and decreases the proportion of the external aldimine of aminoacrylate.

201 ies, which has been assigned as the external aldimine of cystathionine.

202 The internal aldimine of eCGS remains protonated at pH <10.5, and the

203 hase gives an H(+) release when the external aldimine of L-Ser, E(Aex(1)), is converted to E(A-A).

204 nol increases the proportion of the external aldimine of L-serine and decreases the proportion of the

205 inding that the nonionic urea stabilizes the aldimine of L-serine in the presence, but not in the abs

206 dence (1) that the formation of the external aldimine of L-serine is faster than the formation of the

207 mer of the enzyme that predominates when the aldimine of L-serine is formed and shift the equilibrium

208 mer of the enzyme that predominates when the aldimine of L-serine is formed and shifts the equilibriu

209 and increase the proportion of the external aldimine of L-serine.

210 oid intermediate formation from the external aldimine of l-Trp can be estimated to be -26.5 mL/mol, a

211 ogen-bonded ionic contacts hold the external aldimine of PLP and L-alpha-lysine in position for abstr

212 ction, we observed formation of the external aldimine of serine (14 mm(-1) s(-1)) and the aminoacryla

213 intermediate covalently attacks the internal aldimine of the enzyme.

214 sm for TPL involves formation of an external aldimine of the substrate, followed by deprotonation of

215 The internal aldimine of ytCBS remains protonated at pH < 11; therefo

216 hout detectable accumulation of the external aldimine or other intermediates.

217 ic studies suggest that isomerization of the aldimine or resultant iminium to the Z geometry is not a

218 m optically pure N-protected trifluoromethyl aldimines or directly from N-alpha-amino ester trifluoro

219 -OSHS) versus pH profiles can be assigned to aldimine, or to L-OSHS prototropy.

220 he C-P bonds make with the p orbitals of the aldimine pi system are correlated with the reactivities

221 ynthase to close this distance increases the aldimine pK(a) from 9.3 to 10.0, as would be predicted f

222 retro mutation A224I into AATase raised the aldimine pK(a) of that enzyme from 6.96 to 7.16 and resu

223 g 1.1 unit decrease (from 9.3 to 8.2) in the aldimine pK(a), thus identifying Ile232 as a major deter

224 of the succinyl-CoA substrate, the external aldimine predominates over the glycine quinonoid interme

225 aromatic and aliphatic N-tert-butanesulfinyl aldimines proceeds in good yields (up to 97%) and with v

226 with a range of aldehydes to give bidentate aldimine proligands L.

227 methyl acetate, to the N-tert-butanesulfinyl aldimines provides 1,2-disubstituted beta-amino alcohols

228 ization of a range of aromatic ketimines and aldimines provides bi- and tricyclic ring systems with g

229 Its assignment as Ala aldimine, quinonoid, and ketimine forms in rapid equilib

230 he active site lysine and the other with the aldimine reduced to a secondary amine.

231 tive coupling of alcohols and amines to form aldimines represents an environmentally benign methodolo

232 by comparable amounts of the L-Ser external aldimine Schiff base, E(Aex1), and the alpha-aminoacryla

233 to a lysine residue (Lys265) as an internal aldimine/Schiff base and the active site is composed of

234 An assortment of aldimines serve as suitable substrates.

235 tly from N-alpha-amino ester trifluoromethyl aldimines, small psi[CH(CF3)NH]-peptidomimetic backbones

236 Na(+) binding stabilizes the l-Ser external aldimine species, E(Aex(1)).

237 reaction of l-Ser with the MVC-free internal aldimine species, E(Ain), initially gives small amounts

238 in the resting holoenzyme form, the internal aldimine state of tryptophan synthase.

239 Comparison of the l-Ser external aldimine structures of both native and N100Y reveals sig

240 stereoselectivities (>96:2) for a variety of aldimine substrates.

241 ible with stabilization of the GABA external aldimine suggest that a GabR aminotransferase-like activ

242 ociated with Schiff base formation, ketimine/aldimine tautomerization, and transimidation etc.

243 -Cys gives a tautomeric form of the external aldimine that absorbs at 330 nm, and is also seen in the

244 e of PLP and l-threonine reveals an external aldimine that has lost the l-threonine side chain.

245 mase because, upon formation of the external aldimine, the phosphonate group interacts with putative

246 ransfer hydrogenation and hydrosilylation of aldimines through amine-boranes and silanes, respectivel

247 rms: one with the PLP covalently bound as an aldimine to the Nepsilon-amino group of the active site

248 , which must rearrange to a 2-aminocrotonate aldimine to yield final products.

249 ate 2 undergo 1,2-addition with a variety of aldimines to afford the corresponding secondary sulfonam

250 the addition of phosphites to aldehydes and aldimines to give enantioenriched alpha-hydroxy and alph

251 enzyme steers the breakdown of the external aldimine toward decarboxylation instead of amino transfe

252 addition of acetylacetone to N-Boc protected aldimines Type I E and Type II E are active.

253 ituted o-thiomethyl-p-methoxyaniline-derived aldimines undergo Ag-catalyzed enantioselective VM react

254 one-derived titanium enolate and an aromatic aldimine was found to occur only after introduction of a

255 thyl nitroacetate on N-alkyl trifluoromethyl aldimines was reported to synthesize beta-amino alpha-ni

256 zed addition reactions of arylboroxines with aldimines were also realized.

257 L-tyrosine resulted in formation of external aldimine, which absorbed at 420 nm, and a very small abs

258 bsorption of the 423 nm band of the external aldimine, which is a characteristic of the open conforma

259 (pinacolato)diboron to N-tert-butanesulfinyl aldimines, which proceeds in good yields (52-88%) and wi

260 one monomer, the PLP remained as an internal aldimine with a deprotonated Schiff base.

261 The formation of an external aldimine with aspartic acid at pH 9 also produces the ke

262 e of the product acetate and of the external aldimine with l-serine.

263 The inactive enzyme is an aldimine with lambda(max) of 432 nm.

264 K42A-OASS is isolated as an external aldimine with methionine or leucine and shows no reactio

265 Myriocin initially forms an external aldimine with PLP at the active site, and a structure of

266 tion activation via formation of an external aldimine with PLP.

267 inding to SufS and formation of the external aldimine with pyridoxal phosphate required for early ste

268 L-Ala-P forms an external aldimine with the bound pyridoxal 5'-phosphate (PLP) cof

269 saldimination of the PLP-Lys144beta internal aldimine with the PLP-substrate external aldimine.

270 eta subunit Lys(87), which forms an internal aldimine with the pyridoxal phosphate and catalyzes the

271 he complex, L-serine forms a stable external aldimine with the pyridoxal phosphate coenzyme at the ac

272 ymmetric cycloaddition of o-hydroxy aromatic aldimines with 3-substituted coumarins.

273 The reaction of chiral N-tert-butanesulfinyl aldimines with beta-keto acids under basic conditions at

274 for the preparation of a variety of sulfinyl aldimines with excellent yields and purities in only 10

275 h reactions between glycine imines and N-Boc-aldimines with high levels of enantio- and diastereocont

276 ulfate prevent the formation of the external aldimines with L-cysteine or L-serine; (ii) chloride and

277 The mechanism of reaction of N-(3-pyridyl)aldimines with olefins can be explained by an asynchrono

278 Structures of the external aldimines with substrate/product reveal a pair of histid

279 scopes that can catalyze both aldehydes and aldimines with such high selectivity and no reports util

280 nit, in which both amino acids form external aldimines with the coenzyme, pyridoxal phosphate.