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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 reaction after the formation of the external aldimine.
15 ate results in the formation of the external aldimine.
16 hydrogen bonding with the sulfhydryl of Cys-aldimine.
17 nal aldimine with the PLP-substrate external aldimine.
18 0.6 +/- 3.8 s(-1) and re-formed the internal aldimine.
19 racemic donor-acceptor cyclopropanes and (E)-aldimines.
20 use of o-thiomethyl-p-methoxyaniline-derived aldimines.
21 t at room temperature with aldehydes to give aldimines.
22 nation precatalyst of diphenylacetylene with aldimines.
23 broad substrate range including nonaromatic aldimines.
24 hons for enantioselective additions to N-Boc-aldimines.
25 ative to the classical methods for preparing aldimines.
26 e reactions, especially for the synthesis of aldimines.
27 nozinc reagents to a variety of alpha-chloro aldimines.
29 wide range of N-p-(methoxy)phenyl protected aldimines 3 derived from alkyl, aryl, and heteroaryl ald
31 ononitrile and diphenylphosphinoyl-protected aldimine affording products in high yields (up to 98%) a
32 uent radical-radical coupling with secondary aldimines affords a variety of beta-amino ether products
33 ated between the alpha-site and the external aldimine, alpha-aminoacrylate, and quinonoid forms of th
36 bind to the allosteric site in the internal aldimine and alpha-aminoacrylate external aldimine forms
37 the rates of the interconversion of external aldimine and aminoacrylate intermediates in the Tryptoph
38 sition state for interconversion of external aldimine and aminoacrylate intermediates in the Tryptoph
39 and approximately 340 nm, is assigned as Cys aldimine and Cys ketimine forms in rapid equilibrium.
40 ed H123A and C364A SufS variants to trap Cys-aldimine and Cys-ketimine intermediates of the cysteine
41 DAB, and 2,3-DAPr bind to PLP as an external aldimine and elicit the AdoCbl Co-C bond homolysis and t
47 give, as in solution, a mixture of external aldimine and quinonoid intermediates and gem-diamine and
48 l-Met and l-Phe to form mixtures of external aldimine and quinonoid intermediates as in solution.
49 s to form equilibrating mixtures of external aldimine and quinonoid intermediates in rapid-scanning s
50 c evidence for the formation of the external aldimine and quinonoid intermediates in the reactions of
51 rosine form equilibrium mixtures of external aldimine and quinonoid intermediates when they bind to T
52 e to form equilibrating mixtures of external aldimine and quinonoid intermediates, absorbing at appro
53 s to form equilibrating mixtures of external aldimine and quinonoid intermediates, similar to those o
55 ) gives an equilibrating mixture of external aldimine and quinonoid species, E(Aex)(his) and E(Q)(his
56 x with PMP alone as well as the PLP internal aldimine and show that the dimeric structure of WbpE obs
57 ligned with the p orbitals of the conjugated aldimine and thus maximizes stereoelectronic effects.
58 ned to the endocyclic proton of the internal aldimine and to the bridging hydrogen bond, respectively
59 ect to the (hetero)aromatic aldehyde-derived aldimine and tolerates significant variability of the di
60 cycloaddition reaction between N-(3-pyridyl)aldimines and acetylenes where 1,5-naphthyridines are ob
61 d, starting from N-protected trifluoromethyl aldimines and cyclic or acyclic beta-keto esters bearing
62 h formal [2 + 2] cycloadditions with N-tosyl aldimines and formal [4 + 2] cycloadditions with either
66 s been designed and synthesized; its derived aldimines and ketimines have been applied for asymmetric
68 reaction of substituted donors with N-tosyl aldimines and ketimines in high regio-, diastereo-, and
69 Pr)(3) ester enolates to tert-butanesulfinyl aldimines and ketimines provided beta-substituted, alpha
70 alkynes and alpha,beta-unsaturated N-benzyl aldimines and ketimines that proceeds through dihydropyr
71 gh diastereoselectivity to chiral N-sulfinyl aldimines and ketimines to provide alpha-amino amides.
72 for aromatic, heteroaromatic, and aliphatic aldimines and ketimines using ethyl cyanoformate as the
73 The catalyst has a large scope, can reduce aldimines and ketimines, and tolerates a variety of func
75 to be effective in addition to both N-tosyl aldimines and N-tolyl sulfinimines, the latter reaction
78 e Grignard addition to a tert-butanesulfinyl aldimine, and ring closing olefin metathesis as key step
81 nserved, yet the pK(a)'s of the two internal aldimines are 9.3 and 7.0, respectively, to complement t
86 to the unprotonated tautomer of the external aldimine as well as the appearance of a new fluorescent
87 a broad range of trifluoromethyl imines and aldimines as nucleophiles to engage in chemo-, regio-, d
89 also be used for catalytic hydrogenation of aldimines at room temperature via a frustrated Lewis pai
90 els-Alder reactions of the alkyl-substituted aldimines bearing the structurally modified N-aryl unit
99 th PLP, shows slow formation of the external aldimine but does not form the alpha-aminoacrylate inter
100 ample, from additions to protected/activated aldimines), but those involving ketimines are much less
101 erates both tautomeric forms of the external aldimine, but with D-ornithine the equilibrium is shifte
102 gests that the chemical fate of the external aldimine can be redirected by modifications at the N-ter
103 The overall transformation from amines to aldimines can be conveniently performed by a sequential
104 ive Mannich-type reaction of azlactones with aldimines catalyzed by a chiral phosphoric acid is descr
105 h reaction of diazoacetate esters with N-Boc aldimines catalyzed by silver(I) triflate in the presenc
107 on of the Tryptophan synthase L-Ser external aldimine complex at 495 nm, with 420 nm excitation, prov
108 with the substrate, and its product external aldimine complex have been determined at 1.46, 1.8, and
110 by motion of the l-Trp indole moiety of the aldimine complex, contributes to quinonoid intermediate
112 with cysteine or glutamine forming external aldimine complexes, cysteinyl aldimine and glutaminyl al
115 The synthesis features the use of an enolate-aldimine condensation between a chiral glycine aluminum
116 mes were firstly captured by latex beads via aldimine condensation, followed by bio-recognition using
118 ene to alpha-ketoesters or N-benzenesulfonyl aldimines corroborate a catalytic mechanism involving C
121 ydroxylation was shown to alter the divalent aldimine cross-link chemistry of mutant skin collagen.
122 uman breast cancer cells were embedded in 3D aldimine cross-linked collagen matrices and used as an i
123 equent reaction with hydrogen-bond-activated aldimines delivers beta-aminocarbonyl compounds with hig
124 mbination of these effects leads to a stable aldimine derivative and potent inactivation of alanine r
125 reacted with optically pure trifluoromethyl aldimine derived from (R)-alpha-methylbenzylamine, givin
126 a wide range of N-p-methoxyphenyl-protected aldimines, derived from alkyl, aryl and heteroaryl aldeh
127 As expected, BAPN inhibited the formation of aldimine-derived cross-links in collagen, and the constr
128 Borohydride reduction of the native enzymic aldimines did not increase the denaturation temperature
129 ) chloride and sulfate increase the external aldimine dissociation constants for O-acetyl-L-serine, L
130 t, formation of the L-Ser and L-Trp external aldimines E(Aex1) and E(Aex2) at the beta-site causes a
132 nts for the conversion of the L-Ser external aldimine, E(Aex1), to E(A-A) show that the primary kinet
135 (gamma-thialysine) or external (ethylamine) aldimine followed by the slow formation of the alpha-ami
136 mplex and the pyridoxal 5'-phosphate-glycine aldimine, followed by the abstraction of the glycine pro
137 Cys-364 is essential for positioning the Cys-aldimine for Calpha deprotonation, His-123 acts to proto
138 posits two parallel pathways to the external aldimine for this mutant, the minor one has the alpha-am
139 brium isotope effect ((2)H-EIE) favoring the aldimine form (417 nm) is observed in the second state p
140 structure of NtdA alone reveals the internal aldimine form of NtdA with the cofactor pyridoxal phosph
141 udies of the ASL complexes with the internal aldimine form of the enzyme establish the following.
142 ydryl group of the substrate on the internal aldimine form of the pyridoxal 5'-phosphate (PLP) cofact
143 sopropylamine, and glycine all have external aldimine formation as the rapid observable step, based o
147 anism (observed as a lag in the ALA external aldimine formation progress curve), consistent with conf
148 isotope effects were found for the external aldimine formation steps in both the L --> D (1.13 +/- 0
149 The spectral data indicate that external aldimine formation with either AIB or L-alanine and DGD-
150 the progress curve for the L-serine external aldimine formation, indicating a hysteretic behavior in
153 arrangement mechanism, in which the external aldimine formed between PLP and lysine is initially conv
155 situ generation and trapping of the reactive aldimine formed from urea and aldehyde by the diene syst
158 NMR experiments on isotopically labeled PLP aldimines formed by lyophilization with poly-L-lysine.
160 al aldimine and alpha-aminoacrylate external aldimine forms of OASS; (iv) sulfate also binds to the a
161 cient biomimetic method for the synthesis of aldimines from aldehydes and compounds bearing the NH2 g
162 p process involving the initial formation of aldimines from the corresponding aldehydes and 2-amino b
163 range of heteroaromatic and simple aliphatic aldimines gave anti-rich (approximately 3-19:1) beta-nit
164 (dimethylamino)vinyl]-1,3-dimethyluracil and aldimines has been developed for the construction of dih
165 xal 5'-phosphate (PLP) linked as an internal aldimine in alanine racemase (AlaR), aspartate aminotran
166 orption and emission spectra of the internal aldimine in the absence and presence of the product acet
169 n of the roles of aryl nitromethane and aryl aldimine in the key step, which revealed unique substrat
171 ormation of the geminal diamine and external aldimine in this pathway were determined to be 25 and 4
172 e of aryl, heteroaryl, vinyl, or cyclopropyl aldimines in high yield and with excellent diastereo- (u
173 adical rearrangement by forming a lysine-PLP aldimine, in which the imine group participates in the i
174 Mannich (VM) reactions of alkyl-substituted aldimines (including those bearing heteroatom-containing
175 formation (386 s-1 at 0.1 M) of an external aldimine intermediate absorbing at 420 nm, followed by s
177 e, and decanoyl-CoA shows a trapped external aldimine intermediate, suggesting that the condensation
179 demonstrates that formation of the external aldimine intermediates and abstraction of the C alpha pr
180 rt a stepwise racemization of stereoisomeric aldimine intermediates in which a substrate-based carban
181 ble that stereoisomerization of the external aldimine intermediates occurs through a concerted double
182 in of V241 facilitates formation of external aldimine intermediates with primary amine substrates, wh
184 on of N-telopeptide allysine aldol dimers in aldimine intermolecular linkage to nonglycosylated alpha
186 e binding of L-allothreonine as the external aldimine is faster than formation of the 3-methyl aminoa
188 bsorption spectra indicate that the external aldimine is the predominant L-serine intermediate and th
190 lkylation of indole and its derivatives with aldimines is efficiently catalyzed by a zinc-ProPhenol d
192 ogue onto PLP (i.e. formation of an external aldimine) is also rapid (532 s(-1), D-ornithine; 488 s(-
193 We infer that these represent the internal aldimine (lambda(max) 416 nm; A), two different unligand
195 the substrate Calpha-H bond in the external aldimine lies between those of the two catalytic bases,
197 The data indicate that the formation of the aldimine linkage between lysine 346 and PLP is important
198 his is characteristic of the reduction of an aldimine linkage between the carbonyl group of PLP and t
199 scopy with HemA suggested the presence of an aldimine linkage between the enzyme and pyridoxal 5'-pho
200 n a pyridoxal 5'-phosphate (PLP) molecule in aldimine linkage to Lys39 as a protonated Schiff base, a
201 /beta barrel and is covalently linked via an aldimine linkage to Lys39, which is at the C-terminus of
202 radical rearrangement by forming an external aldimine linkage with the epsilon-amino group of a subst
203 amides by intramolecular ring closure of the aldimine moieties with the carboxamide group elicited by
204 ex with the reduced analogue of the external aldimine, N-(5'-phosphopyridoxyl)-d-alanine (PPDA).
205 the phenolic oxygen (enolimine form) to the aldimine nitrogen (ketoenamine form) is often considered
206 7.7) from a form with a protonated internal aldimine nitrogen (lambdamax = 416 nm) to a deprotonated
207 phosphate, reducing the pKa of the internal aldimine nitrogen and promoting formation of quinonoid i
209 l-depleted enzyme, formation of the external aldimine occurs over long time scales (approximately 50
210 ional change induced by the formation of the aldimine of 4-aminocyclopentane-1,3-dicarboxylic acid an
211 mM) decrease the proportion of the external aldimine of aminoacrylate and induce formation of the qu
212 We find that the gem-diamine and external aldimine of aminoacrylate are the primary intermediates
213 reaction with L-serine and that the external aldimine of aminoacrylate or its complex with L-homocyst
214 n the absence of L-homocysteine produced the aldimine of aminoacrylate, which absorbed at 460 nm and
218 hase gives an H(+) release when the external aldimine of L-Ser, E(Aex(1)), is converted to E(A-A).
219 nol increases the proportion of the external aldimine of L-serine and decreases the proportion of the
220 inding that the nonionic urea stabilizes the aldimine of L-serine in the presence, but not in the abs
221 dence (1) that the formation of the external aldimine of L-serine is faster than the formation of the
222 mer of the enzyme that predominates when the aldimine of L-serine is formed and shift the equilibrium
223 mer of the enzyme that predominates when the aldimine of L-serine is formed and shifts the equilibriu
225 oid intermediate formation from the external aldimine of l-Trp can be estimated to be -26.5 mL/mol, a
226 ogen-bonded ionic contacts hold the external aldimine of PLP and L-alpha-lysine in position for abstr
227 ction, we observed formation of the external aldimine of serine (14 mm(-1) s(-1)) and the aminoacryla
229 sm for TPL involves formation of an external aldimine of the substrate, followed by deprotonation of
232 ic studies suggest that isomerization of the aldimine or resultant iminium to the Z geometry is not a
233 m optically pure N-protected trifluoromethyl aldimines or directly from N-alpha-amino ester trifluoro
235 he C-P bonds make with the p orbitals of the aldimine pi system are correlated with the reactivities
236 ynthase to close this distance increases the aldimine pK(a) from 9.3 to 10.0, as would be predicted f
237 retro mutation A224I into AATase raised the aldimine pK(a) of that enzyme from 6.96 to 7.16 and resu
238 g 1.1 unit decrease (from 9.3 to 8.2) in the aldimine pK(a), thus identifying Ile232 as a major deter
239 of the succinyl-CoA substrate, the external aldimine predominates over the glycine quinonoid interme
240 aromatic and aliphatic N-tert-butanesulfinyl aldimines proceeds in good yields (up to 97%) and with v
241 ta support the irreversible formation of the aldimine product in marked contrast with traditional met
244 methyl acetate, to the N-tert-butanesulfinyl aldimines provides 1,2-disubstituted beta-amino alcohols
245 ization of a range of aromatic ketimines and aldimines provides bi- and tricyclic ring systems with g
249 tive coupling of alcohols and amines to form aldimines represents an environmentally benign methodolo
250 by comparable amounts of the L-Ser external aldimine Schiff base, E(Aex1), and the alpha-aminoacryla
251 to a lysine residue (Lys265) as an internal aldimine/Schiff base and the active site is composed of
253 tly from N-alpha-amino ester trifluoromethyl aldimines, small psi[CH(CF3)NH]-peptidomimetic backbones
255 reaction of l-Ser with the MVC-free internal aldimine species, E(Ain), initially gives small amounts
259 ible with stabilization of the GABA external aldimine suggest that a GabR aminotransferase-like activ
261 -Cys gives a tautomeric form of the external aldimine that absorbs at 330 nm, and is also seen in the
263 mase because, upon formation of the external aldimine, the phosphonate group interacts with putative
264 ransfer hydrogenation and hydrosilylation of aldimines through amine-boranes and silanes, respectivel
265 rms: one with the PLP covalently bound as an aldimine to the Nepsilon-amino group of the active site
267 re diastereoselective additions to aldehydes/aldimines to access homoallylic alcohols/amines containi
268 ate 2 undergo 1,2-addition with a variety of aldimines to afford the corresponding secondary sulfonam
269 the addition of phosphites to aldehydes and aldimines to give enantioenriched alpha-hydroxy and alph
270 enzyme steers the breakdown of the external aldimine toward decarboxylation instead of amino transfe
272 ituted o-thiomethyl-p-methoxyaniline-derived aldimines undergo Ag-catalyzed enantioselective VM react
273 one-derived titanium enolate and an aromatic aldimine was found to occur only after introduction of a
274 thyl nitroacetate on N-alkyl trifluoromethyl aldimines was reported to synthesize beta-amino alpha-ni
276 L-tyrosine resulted in formation of external aldimine, which absorbed at 420 nm, and a very small abs
277 bsorption of the 423 nm band of the external aldimine, which is a characteristic of the open conforma
278 (pinacolato)diboron to N-tert-butanesulfinyl aldimines, which proceeds in good yields (52-88%) and wi
286 inding to SufS and formation of the external aldimine with pyridoxal phosphate required for early ste
289 eta subunit Lys(87), which forms an internal aldimine with the pyridoxal phosphate and catalyzes the
290 he complex, L-serine forms a stable external aldimine with the pyridoxal phosphate coenzyme at the ac
292 tion of in situ generated heterocyclic azine-aldimines with B-keto sulfoxonium ylides has been develo
293 The reaction of chiral N-tert-butanesulfinyl aldimines with beta-keto acids under basic conditions at
294 for the preparation of a variety of sulfinyl aldimines with excellent yields and purities in only 10
295 h reactions between glycine imines and N-Boc-aldimines with high levels of enantio- and diastereocont
296 ulfate prevent the formation of the external aldimines with L-cysteine or L-serine; (ii) chloride and
297 The mechanism of reaction of N-(3-pyridyl)aldimines with olefins can be explained by an asynchrono
299 scopes that can catalyze both aldehydes and aldimines with such high selectivity and no reports util