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1 )(CH(3))P, where NHC(R) is an N-heterocyclic carbene).
2 a highly sterically hindered N-heterocyclic carbene.
3 penes give dimerizations of the intermediate carbene.
4 rdination sites and the first true dianionic carbene.
5 cult functional groups to be appended to the carbene.
6 y means of C-H insertion with donor/acceptor carbenes.
7 lylation reaction and migratory insertion of carbenes.
8 lts in nitrogen elimination and formation of carbenes.
9 tures that influence the stability of siloxy carbenes.
10 val those of ylide-stabilized N-heterocyclic carbenes.
11 IM) with two representative isolable singlet carbenes.
12 of a large variety of pyridinium salts with carbenes.
13 fragments, such as carbodiphosphoranes and -carbenes.
14 and a vacant orbital, reminiscent of singlet carbenes.
15 es are consistent with those of nucleophilic carbenes.
16 tion chemistry of oxidatively generated gold carbenes.
17 metric redox-active Au(I) bis-N-heterocyclic carbenes.
18 l for scaling the pai-accepting character of carbenes.
19 thus genuinely making it isoelectronic with carbenes.
22 zol-2-ylidene (IPr) and cyclic (alkyl)(amino)carbene (2,6-diisopropylphenyl)-4,4-diethyl-2,2-dimethyl
23 n we report that a stable singlet ambiphilic carbene activates CO and catalytically promotes the carb
25 ively and covers the usage of N-heterocyclic carbene adducts of the p-block elements as ligands in tr
26 possible modifications that could improve Au-carbene affinity and specificity for G-quadruplex bindin
27 e order Ag < Au < Cu, with the lifetimes of (carbene)Ag(Cz) roughly a factor of 10 shorter than for (
29 carbazolyl) (M(MAC)) complexes show coplanar carbene and carbzole ligands and C-M-N bond angles of ~1
30 ed to show competitive production of singlet carbene and ketene intermediates from the photoexcitatio
34 lopment of this chemistry are donor/acceptor carbenes and the chiral dirhodium tetracarboxylate catal
35 arate sections including generation of vinyl carbenes and their reactions, metathesis processes, hete
37 l-enones were reacted with an N-heterocyclic carbene, and an intramolecular Stetter reaction proceede
40 and reduced pnictonium-stabilisation of the carbene as group 15 is descended, which is supported by
42 p = 2,6-iPr(2)C(6)H(3); NHC = N-heterocyclic carbene] as red crystalline solids containing a pai-dono
45 synthesis of storable bicyclic (alkyl)(amino)carbenes (BICAACs), which feature enhanced sigma-donatin
47 ter understand the molecular mechanism of Au-carbene binding to G-quadruplexes, we employed molecular
49 l ligands including thiols and amines, metal-carbene bonds that are stable under reductive potentials
50 molysis in the presence of an N-heterocyclic carbene borane (NHC-borane) and di-tert-butyl peroxide.
57 s productivity of leading cyclic alkyl amino carbene (CAAC) catalysts relative to their important N-h
58 )Br(4) coordinated by a cyclic (alkyl)(amino)carbene (cAAC) in a 3:1 ratio affords a neutral tetrabor
59 e 2 was converted to a cyclic (alkyl) (amino)carbene (cAAC) via 1,2-hydrogen migration triggered by b
60 able boraphosphaketene, cyclic(alkyl)(amino) carbene (CAAC)-borafluorene-P=C=O (2), is described.
61 clic carbene (NHC)- and cyclic (alkyl)(amino)carbene (CAAC)-stabilized borafluorene radicals have bee
62 zed by a state-of-the-art cyclic alkyl amino carbene (CAAC, C1) and a bridging chloride donor: the la
63 cyclic (amino)(alkyl), monoamido, or diamido carbenes (CAAC, MAC, or DAC, respectively) as chromophor
65 arbene carbon centre in cyclic (alkyl)(amino)carbenes (CAACs) is known to exhibit transition-metal-li
67 r(I) complexes bearing a cyclic (amino)(aryl)carbene (CAArC) ligand with various complex geometries h
69 monstrated that stable singlet electrophilic carbenes can behave as metal surrogates in the activatio
70 choice: the resulting piano-stool ruthenium carbenes can engage a tethered alkene into either cyclop
72 or ylide formation by singlet alpha-carbonyl carbene capture in aprotic nucleophilic solvents (with y
73 strategy, one of the hallmarks of alpha-oxo carbene/carbenoid chemistry, that is, the Wolff rearrang
75 fords a transfer of nucleophilicity from the carbene carbon atom to the attached exocyclic moiety, an
77 g interest in reactive intermediates such as carbenes, carbon radicals, carbanions, and carbocations.
80 thenium 2,2':6',2"-terpyridine (tpy) pyridyl-carbene catalysts reveals the importance of stereochemic
81 ability to access both enantiomers from the carbene-catalyzed reaction is a powerful strategy that c
82 d 1,4-diketones has been developed through a carbene-catalyzed Stetter reaction of vinylphosphonates
83 lations reveal that this gives unprecedented carbene character to the P-C-O unit, which engages in a
85 This approach opens a new horizon for the carbene chemistry to modify silver nanoparticles with va
86 carbenes are relatively new in the field of carbene chemistry; although applications in C-H and X-H
87 as well as to the stability of the secondary carbene complex formed, if metathesis were to take place
88 Here, we report that treatment of a uranium-carbene complex with an organoazide produces a uranium(V
94 ent herein anionic borate-based bi-mesoionic carbene compounds of the 1,2,3-triazol-4-ylidene type th
96 ne moieties can allow access to unusual free carbene coordination geometries given the proper stabili
98 r modest activation barriers, and the latter carbenes cyclize very easily to 2 H- and 3 H-indazoles,
99 entally demonstrate that the smallest cyclic carbene, cyclopropenylidene, binds even more strongly th
100 .g. as accomplished for cyclopentadienyl and carbene derivatives) and a rewarding collaboration betwe
102 arboxylates catalyze an Si-H insertion using carbenes derived from diazo compounds where selective fo
103 silyl ethers was achieved using rhodium(II) carbenes derived from N-sulfonyltriazoles and aryldiazoa
104 anometallic complexes since the 1960s, these carbenes did not attract considerable attention until Ar
106 esses involving the iron(III) N-heterocyclic carbene (FeNHC) photosensitizer [Fe(phtmeimb)(2)](+) (ph
107 carbenoids leads to the formation of singlet carbenes followed by their trapping via an intramolecula
108 ue-level resolution enabled by IM-MS-coupled carbene footprinting can bridge the gap between structur
111 Tricyclo[2.1.0.0(2,5)]pent-3-ylidene is a carbene foreseen to rearrange to pyramidane (c-C(4)H(4))
112 e deprotonated by hydroxide ions, leading to carbenes formation that self-assembled on the electrode'
115 volution toward more challenging heterocycle carbene functionalizations, including C(2)/ C(3) regiose
117 apping platform that exploits photocatalytic carbene generation to selectively identify protein-prote
118 yst-antibody conjugate to spatially localize carbene generation, we demonstrate selective labeling of
120 ursor, but procedures using diazo-free metal carbenes have been developed with significant success.
121 ent species carrying a divalent carbon atom, carbenes have emerged as key reactive intermediates in o
122 d by taking advantage of NHC (N-heterocyclic carbene, here IDipp) coordination to the low-valent phos
124 ending on the involved catalytic system, the carbene insertion can efficiently be driven towards a sp
125 selectively catalyze cyclopropene formation, carbene insertion into a propargylic C-H bond or [3 + 2]
126 on from the T(1) state of acylsilane and the carbene insertion into the B-H bond occurred in a concer
130 Mechanistic studies reveal that a metal carbene intermediate is not part of the catalytic cycle.
131 c reaction of styrene with the alkenyl-Au(I) carbene intermediate to afford the cis-disubstituted cyc
132 , this transformation does not proceed via a carbene intermediate, nor does it require the presence o
133 ial precursors to generate alpha-imino metal-carbene intermediates and applied in direct C-H function
134 fer direct access to reactive alpha-oxo gold carbene intermediates from benign and readily available
135 ansfer reactions of diazo compounds via free carbene intermediates have emerged as a practical, mild
136 red heme enzymes that can insert fluoroalkyl carbene intermediates into alpha-amino C( sp(3))-H bonds
137 stepwise mechanism proceeds through singlet carbene intermediates which can also participate in bimo
138 generated systems catalyze the insertion of carbenes into the C-H bonds of a range of phthalan deriv
139 al approach that now allows the insertion of carbenes into the Si-H bond of silanes under metal-free
144 Li enolates to a roughly sp(2) type in their carbene keto tautomers, is recognized in one of these pa
145 rinting strategy based on the discovery that carbene labeling produces subresidue peptide isomers and
148 locate the strongly donating N-heterocyclic carbene ligand trans to the site of CO(2) activation.
149 ere synthesized with the tris-N-heterocyclic carbene ligand tris[2-(3-mesitylimidazol-2-ylidene)ethyl
151 nally, pairing the strongly donating pyridyl-carbene ligand with the redox-active tpy ligand proves t
155 ommon amide (N-carbazolyl) and two different carbene ligands (i.e., CAAC = (5 R,6 S)-2-(2,6-diisoprop
157 ulations on duplex DNA in the presence of Au-carbene ligands indicates a preference for the minor gro
161 Whereas very restricted mobility of two Au-carbene ligands was found upon binding as a doublet to o
163 gated bearing nonconventional N-heterocyclic carbene ligands, monoamido-aminocarbene (MAC*) and diami
166 tiple bond to give, after rearrangement, the carbene-ligated Al(III) amide, NacNac'Al(NHTol)(SIMe) (6
167 Reactivity studies of 3 corroborate its carbene-like nature: protonation with [LutH]I results in
170 ovel, redox-active bipyridyl- N-heterocyclic carbene macrocyclic ligand complexed with nickel, CO(2)
172 on, the first examples of the gold mesoionic carbene mediated [2+2+2] cycloaddition of these enynes w
173 zed Conia ene reaction and an N-heterocyclic carbene-mediated acyloin addition to rapidly fashion its
180 l molybdenum imido alkylidene N-heterocyclic carbene (NHC) bistriflate and monotriflate monoalkoxide
181 inone methides (aza-o-QMs) by N-heterocyclic carbene (NHC) catalysis has been discovered and explored
182 ediated metalation (AMMM) and N-heterocyclic carbene (NHC) chemistry, a novel C-N bond activation and
184 tom abstraction from a set of N-heterocyclic carbene (NHC) complexes of alkenylboranes bearing two te
186 The remarkable resilience of N-heterocyclic carbene (NHC) gold bonds has quickly made NHCs the ligan
189 The use of an electron-rich N-heterocycilc carbene (NHC) ligand is effective to inhibit undesired b
190 omplex bearing an unsaturated N-heterocyclic carbene (NHC) ligand, for the first time, products deriv
192 ring C(1)- and C(2)-symmetric N-heterocyclic carbene (NHC) ligands were prepared from prochiral NHC p
194 c molybdenum imido alkylidene N-heterocyclic carbene (NHC) monotriflate complex with 2-methoxystyrene
195 turated 2,6-diisopropylphenyl N-heterocyclic carbene (NHC) precursors with excellent selectivity (up
196 s relative to their important N-heterocyclic carbene (NHC) predecessors, as recently demonstrated in
197 the reaction proceeds via an N-heterocyclic carbene (NHC) siloxygermylene [(NHC)RGe(OSiHPh(2))].
198 lting from the addition of an N-heterocyclic carbene (NHC) to benzaldehyde triggers a fast deprotonat
199 ans effect of picoline vs the N-heterocyclic carbene (NHC) was quantified through a kinetic analysis
201 radicals derived from alkenyl N-heterocyclic carbene (NHC)-boranes bearing ester substituents were re
202 ilable alkenyl triflates with N-heterocyclic carbene (NHC)-boranes in the presence of diisopropyl eth
205 The reductive coupling of a N-heterocyclic carbene (NHC)-stabilized aryldibromoborane yields a mixt
206 port the use of two polymeric N-heterocyclic carbenes (NHC) (polydentate and monodentate) to stabiliz
208 from readily available chiral N-heterocyclic carbenes (NHCs) and chiral diamines is disclosed for the
211 s such as bulky phosphines or N-heterocyclic carbenes (NHCs) has enabled reactions of unactivated alk
212 unctional theory computations.N-heterocyclic carbenes (NHCs) have been applied as ancillary ligands i
216 dinating dianionic carboranyl N-heterocyclic carbenes (NHCs) to create organometallic -ate complexes
218 nt in functionalizing gold by N-heterocyclic carbenes (NHCs), a promising alternative ligand class re
219 disubstituted imidazolylidene N-heterocyclic carbenes (NHCs), where the 4,5-substituents are Me, H, o
223 -diisopropylphenyl (Dip); D = N-heterocyclic carbene or 4-dimethylaminopyridine, DMAP), which X-ray c
224 leads to the formation of either MCH(2) (+) carbene or HMCH(+) carbyne hydride structures, the obser
225 ration of surface modification with a stable carbene other than NHC; more broadly, it drives further
226 nt can be readily realized by alpha-oxo gold carbenes oxidatively generated from TBS-terminated alkyn
227 e research efforts, the synthesis of iron PC(carbene)P pincer complexes has so far remained elusive.
229 fin monomers; however, controlled and living carbene polymerization has been a long-standing challeng
231 mers, which polymerize ethyl diazoacetate, a carbene precursor in a controlled and quasi-living manne
232 is enables the use of [1.1.1]propellane as a carbene precursor in cyclopropanations of a range of fun
233 mechanophore built around an N-heterocyclic carbene precursor proceeds with the rupture of a C-C bon
234 cally involve the formation of a diazo-based carbene precursor, but procedures using diazo-free metal
238 )(2)Be](+*) (2) [CAAC = cyclic (alkyl)(amino)carbene], prepared by oxidation of a zero-valent berylli
239 sertion reactions with donor/donor and donor carbenes, providing context for future developments in t
240 two N-(2-pyridyl)-substituted N-heterocyclic carbene (PyNHC) ligands in a bidentate fashion in additi
242 -mediated pathway for singlet alpha-carbonyl carbene reaction with alcohols (ethanol or tert-butanol)
245 es and their tendency for dimerization, free carbenes represent one of the foremost obscured classes
246 between catalysts containing large and small carbenes results more from stabilizing intramolecular no
248 jugation, can play a significant role in the carbene-selenium (77) Se NMR chemical shift, thus trigge
251 ought to proceed via the formation of Rh(II) carbene species followed by interaction with the Lewis b
256 represents the unprecedented utilization of carbene-stabilized disilicon (1) as a silicon-transfer a
259 r level and expanded to higher-order homolog carbenes such as butadiynylcyclopropenylidene and triple
260 sion that other phosphine and N-heterocyclic carbene, such as P (n)BuAd(2) and IMes, can be used as a
262 signed redox-active Au(I) bis-N-heterocyclic carbene that induces ICD both in vitro and in vivo.
263 Hence, drug molecules such as gold (Au)-carbene that stabilize G-quadruplexes may also interfere
264 insight into the properties of this class of carbenes, the thermodynamic stabilities of a series of k
266 ient rhodium-catalyzed insertion of azavinyl carbenes to C3-H bond of indole followed by base-mediate
267 bicyclic aziridines and rhodium-bound vinyl carbenes to form complex dehydropiperidines in a highly
268 ts of intra/intermolecular azo coupling, and carbenes to give pyrrole-containing insertion products i
269 d stereoselective intermolecular transfer of carbenes to olefins, heterocycles, aldehydes, and amines
270 highlight the ability of these Fischer-type carbenes to participate in cascade alternating ring-open
273 ed from sperm whale myoglobin that exploit a carbene transfer mechanism for the asymmetric synthesis
274 reactions of onium ylides via gold catalyzed carbene transfer reactions are relatively unexplored.
279 lving a cytochrome P450 for highly efficient carbene transfer to indoles, pyrroles, and cyclic alkene
283 tunable active-site geometries, hemoprotein "carbene transferases" could provide an alternative to tr
284 fective chiral catalyst for triazole-derived carbene transformations, whereas Rh(2) (S-TPPTTL)(4) wor
286 nglet ethynylcyclopropenylidene (c-C(5)H(2)) carbene-via the elementary reaction of the simplest orga
289 dimNHCGe (5, dimNHC = diimino N-heterocyclic carbene) was successfully prepared via the reduction of
290 he enhanced stability imparted by ambiphilic carbenes, we report and rationalize the absolute templat
291 amic stabilities of a series of known siloxy carbenes were explored on the basis of hydrogenation ent
292 rates were then exposed to an N-heterocyclic carbene, whereupon intramolecular Stetter reaction proce
293 ohols, as it requires the interaction of the carbene with a protic solvent molecule being part of a h
294 r the reaction of the singlet alpha-carbonyl carbene with methanol shows that the enol forms without
296 indicate that 3 is best described as a free carbene with partial Ti-C(beta) bonding that results fro
297 tathesis catalyst bearing two N-heterocyclic carbenes with an oxidizing pyrylium photocatalyst afford
298 s-phase chemistry of preparing two prototype carbenes with distinct multiplicities-triplet pentadiyny
299 ands, 23 bidentate P,P-donor ligands, and 30 carbenes, with a view to providing a useful resource for
300 l (using dispersion-corrected DFT) on siloxy carbenes (X-C-OSiR(3), singlet and triplet state), oxoca