ライフサイエンスコーパス: carbenoid

1 mining step is the generation of the rhodium carbenoid.

2 etylenic pi-bond to generate a cycloalkenone carbenoid.

3 ically generated transition metal carbene or carbenoid.

4 on reaction with a tertiary amine containing carbenoid.

5 lver-bound aryl cation or 1,2-carbene-silver carbenoid.

6 oid and the approach of the substrate to the carbenoid.

7 r C-H insertions with donor/acceptor rhodium carbenoids.

8 osphoric acid-cocatalyzed insertion of metal carbenoids.

9 ster homologation with enantiopure magnesium carbenoids.

10 reactions with acceptor-substituted rhodium carbenoids.

11 synthesis and iterative insertion of various carbenoids.

12 m alkyl, aryl, and formyl aldehydes via zinc carbenoids.

13 with the standard O-H insertion reaction of carbenoids.

14 how the ambiphilic behavior of PhCLiRCN as a carbenoid (11) or a carbanion (9) and the importance of

15 Lastly, when Li-carbenoid 5 is treated directly with CuCl, a double tran

16 ated to afford the corresponding bis(NHC) Li-carbenoid 5 that also displays unique reactivity.

17 le formed by cyclopropanation of the rhodium carbenoid across the aromatic pi-bond.

18 is a three-step process involving a stepwise carbenoid addition of nitrile oxide to form a bicyclic n

19 s was found to be a key factor in successful carbenoid addition, as demonstrated by conducting the re

20 t possible to detect products derived from a carbenoid/alkyne cascade sequence as had previously been

21 The use of magnesium carbenoids allows carbon chains to be grown with the inc

22 formation between the alcohol oxygen and the carbenoid and hydrogen bonding of the alcohol to a carbo

23 e process has proven general with a range of carbenoid and isoxazole components and represents a uniq

24 pathway indicate the intermediacy of rhodium carbenoid and metallocyclobutane species.

25 e active site of the protoglobin forced iron-carbenoid and substrates to adopt a pro-cis near-attack

26 ligands rotate outward to make room for the carbenoid and the approach of the substrate to the carbe

27 y electronically stabilized lithium chloride carbenoids and affords a variety of different diphosphin

28 ore via formal [5+2] cycloaddition of styryl carbenoids and aldehydes significantly expands the arsen

29 By changing the leaving groups of the carbenoids and altering Lewis acid activators, selective

30 rearrangement between donor/acceptor rhodium carbenoids and chiral allyl alcohols is a convergent C-C

31 nsertion chemistry as long as donor/acceptor carbenoids and highly substituted allyl alcohols are use

32 mixed aggregates between chloromethyllithium carbenoids and lithium dimethylamide (LiDMA).

33 rearrangement is favored with donor/acceptor carbenoids and more highly functionalized propargylic al

34 h E/Z=5:95 by a like combination of Li and B carbenoids and syn (thermal) elimination whereas the E i

35 to rhodium, loss of N(2) to afford a rhodium carbenoid, and an asynchronous but concerted cyclopropan

36 ve intermediates in synthesis (bismetalated, carbenoid, and oxenoids species) becomes now an indispen

37 xtrusion, addition of amine to the dirhodium carbenoid, and the enol formation), except that in the s

38 Siloxy group migration: A rhodium(II) carbenoid approach has been developed for the synthesis

39 s-Block metal carbenoids are carbene synthons and applied in a myriad

40 Carbenes and carbenoids are commonly employed for the synthesis of cy

41 fluoromethyllithium and chloromethyllithium carbenoids are studied in the gas phase and in dimethyl

42 s a D(2)-symmetric arrangement, but when the carbenoid binds to the catalyst, two of the p-bromopheny

43 al carbonium ylide C(+)(BCH(3))(11)(-) and a carbenoid C(BCH(3))(11) whose electronic ground state re

44 termediate by sequential deployment of metal carbenoid C-H insertion and ylide-forming reactions and

45 ected 3(2H)-furanones formed by conventional carbenoid C-H insertion.

46 The topics treated include carbenoids, carbenic philicity, absolute rates of carben

47 trigonal planar ligand environment of three carbenoid carbon centers and an additional, weak axial n

48 ism, in which the nucleophilic attack of the carbenoid carbon of DFAY on the electrophilic carbonyl c

49 ve O-cyclization of the amido group onto the carbenoid center occurs to generate a seven-ring carbony

50 y structures and DFT calculations indicate a carbenoid character of quaternized pyridine-based PCP-Ru

51 Here, we report that Rh-carbenoid chemistry can be used to insert carboxylic est

52 ynthesis of a compound library using rhodium carbenoid chemistry to access structurally diverse three

53 wever, one of the hallmarks of metal carbene/carbenoid chemistry, i.e., insertion into an unactivated

54 y, one of the hallmarks of alpha-oxo carbene/carbenoid chemistry, that is, the Wolff rearrangement, h

55 d for the first time in the context of metal carbenoid chemistry.

56 Two carbenoids combine to generate an olefin by a mechanism

57 mplex represents the first example of a gold carbenoid complex that lacks conjugated heteroatom stabi

58 nucleophilic attack of indazolone on the Pd-carbenoid complex, and intramolecular ring expansion via

59 at a highly reactive phenylpropargyl-gold(I) carbenoid complex, generated from propargyl acetal.

60 sing promiscuous intermolecular reactions of carbenoid compounds enabled highly efficient exploration

61 ted by Lewis acids or base, as well as metal-carbenoid conditions.

62 a key 1,3-dipolar cycloaddition between a Au carbenoid-containing carbonyl ylide and ethyl vinyl ethe

63 d cyclic enediynes were prepared with use of carbenoid coupling strategy.

64 two-step procedure "imine formation/azirine-carbenoid coupling" has been developed for the preparati

65 tric aniline precursor of the N-heterocyclic carbenoid CuIPhEt.

66 tions and inconvenience still exist with the carbenoids currently employed, such as the use of highly

67 dealing with the Cu(II)- or Rh(II)-catalyzed carbenoid cyclization/cycloaddition cascade of several a

68 The Rh(2)(OAc)(4)-stabilized carbenoid derived from dimethyl diazomalonate has been f

69 The metallo carbenoid derived from the D/A diazo group is preferenti

70 lective O-H insertion reactions with rhodium carbenoids derived from alkynyl diazo acetates.

71 compared to the traditionally used acceptor carbenoids derived from unsubstituted diazo esters.

72 elying on the catalytic ability of dirhodium carbenoid (derived from rhodium(II) tetracarboxylate and

73 een demonstrated that donor/acceptor rhodium carbenoids display potential energy activation barriers

74 nstrates that the donor/acceptor-substituted carbenoids display remarkable chemoselectivity, which al

75 mpounds for the generation of reactive metal carbenoids during the past decades.

76 erted (double) C-C bond cleavage and rhodium carbenoid formation, driven by strain-release.

77 w that designed stable, highly electrophilic carbenoid fragments in compounds 4 and 6 can achieve thi

78 include the deacetylation of methyl ketones, carbenoid-free formal homologation of aliphatic linear k

79 ggered by the direct generation of a rhodium carbenoid from 1-sulfonyl-1,2,3-triazole, the highly dia

80 of the alkyl or allyl halide to the rhodium carbenoid from the iodonium ylide to yield a halonium in

81 l-catalyzed conditions for the generation of carbenoids from alpha-diazocarbonyl compounds.

82 The coupling of rhodium carbenoids from vinyl diazoacetates with 2-thio-3-alkyl

83 ioselective redox-neutral cascade process of carbenoid functionalization followed by dephosphonylativ

84 (phosphanyl)phosphaketenes with the gallium carbenoid Ga(Nacnac) (Nacnac=HC[C(Me)N(2,6-i-Pr(2) C(6)

85 tetrahydropyranol; (ii) reaction of a metal carbenoid, generated from a diazo ketone, with an ether

86 a cascade process involving base-mediated Pd-carbenoid generation by the decomposition of N-tosylhydr

87 ircumstances and particularly in cases where carbenoid generation is effected using an electron-defic

88 favored irrespective of the complex used for carbenoid generation or the substitution pattern of the

89 The carbenoid geometries are dependent on the heteroatom and

90 ucts, and sequential insertions of different carbenoids have also been achieved.

91 as the corresponding copper- or silver-bound carbenoids, have been prepared.

92 symmetric insertion reactions of donor-donor carbenoids, i.e., those with no pendant electron-withdra

93 tryptophan modification method using rhodium carbenoids in aqueous solution, allowing the reaction to

94 igands (TACLs) on the selectivity of rhodium carbenoids in competitive cyclopropanation reactions.

95 is and methods to generate sp(3) -hybridized carbenoids in stereodefined form are surveyed.

96 thium (t-BuLi) and magnesium (i-PrMgCl.LiCl) carbenoids in the presence of boronic esters, thus allow

97 The C-H activation is caused by a rhodium carbenoid induced C-H insertion.

98 tivation of silyl ethers by means of rhodium carbenoid-induced C-H insertion represents a very direct

99 enzylic C-H activation by means of a rhodium-carbenoid-induced C-H insertion.

100 rtion followed by controlled mono- or double-carbenoid insertion has been realized with widely availa

101 Carbenoid insertion into boronate carbon-boron bonds, na

102 d an efficient catalyst for enantioselective carbenoid insertion into Si-H bonds.

103 A Pd-catalyzed C(sp(3))-H functionalization/carbenoid insertion is described.

104 Aside from the well-known carbenoid insertion pathways, both beta-elimination and

105 An efficient copper-catalyzed carbenoid insertion reaction of alpha-diazo carbonyl com

106 highly stereoselective intramolecular metal carbenoid insertion reaction of sulfinimine-derived delt

107 site selectivity is determined in the Rh(II)-carbenoid insertion step, which prefers insertion into h

108 ic O-alkylation of sugar-derived lactols via carbenoid insertion to the anomeric OH bond.

109 uces the first example of a biocatalytic N-H carbenoid insertion with an acceptor-acceptor carbene do

110 into the indole C-2 position, through copper-carbenoid insertion.

111 udies dealing with the rhodium(II)-catalyzed carbenoid insertion/cyclization/cycloaddition cascade of

112 wn as the Matteson reaction, involves formal carbenoid insertions into C-B bonds.

113 reaction that enables sequential oxygen and carbenoid insertions into diverse alkyl- and arylboronat

114 he development of aza-Matteson reactions via carbenoid insertions into the N-B bonds of aminoboranes.

115 ether is added, the initially formed rhodium carbenoid intermediate can be intercepted by the electro

116 ide instead undergoes alpha-elimination to a carbenoid intermediate in nonpolar solvents due to the u

117 substrate, we also trapped the reactive iron-carbenoid intermediate involved in this engineered ApePg

118 volving addition of the 1,3-dipole to a gold-carbenoid intermediate is proposed.

119 e, which proceeds via alpha-elimination to a carbenoid intermediate similar to that obtained from 3,

120 we report the generation of a metastable Rh2-carbenoid intermediate supported by a donor-acceptor car

121 (2) reacts with Rh porphyrins via a putative carbenoid intermediate to form cyclopropanation product

122 The reactivity of the Rh-carbenoid intermediate was explored using the ratio of t

123 oceeds by the initial generation of a copper carbenoid intermediate which cyclizes onto the adjacent

124 t time, iodonium ylide proceeds through a Ru-carbenoid intermediate.

125 Along these lines, carbenes and carbenoid intermediates are particularly attractive, but

126 pounds greatly decreases the tendency of the carbenoid intermediates formed during Rh(II)-catalyzed r

127 termediacy of highly reactive, electrophilic carbenoid intermediates that have eluded direct observat

128 fluxional nature of gold(I)-stabilized vinyl carbenoid intermediates.

129 oups via Rh(II)-catalyzed insertion of metal carbenoid intermediates.

130 electrophilicity between the various rhodium carbenoid intermediates.

131 bonds through insertion of rhodium azavinyl carbenoid into a N-H bond followed by cyclization and ar

132 ducts resulting from formal insertion of the carbenoid into an aromatic C-H bond were detected.

133 ongested amines, with insertion of a rhodium carbenoid into an N-H bond as the key step, is described

134 n azetidinone derived by CH-insertion of the carbenoid into the neighboring benzyl group.

135 The intramolecular insertion of rhodium carbenoids into the alpha-C-H bonds of allylic ethers to

136 -Smith reaction using a novel boromethylzinc carbenoid is described.

137 Although the carbenoid is generated in the presence of a 1:2 mixture

138 dride migration to the rhodium center of the carbenoid is operative.

139 ute to the reactivity of the intermediate Rh-carbenoid is presented.

140 active handles for modification with rhodium carbenoids is also reported.

141 vailable alpha-boryl pyrrolidines with metal carbenoids is especially challenging even when good leav

142 e stereoselective transfer of functionalized carbenoids is one of the most significant deficiencies o

143 merization and eliminative cross-coupling of carbenoids is reviewed with a range of illustrative exam

144 s showed that formal migration to the distal carbenoid isomer and subsequent trapping had occurred.

145 m that favors the formation of monoalkylzinc carbenoid IZnCH2I relative to dialkylzinc carbenoid Zn(C

146 clopropanation of an alpha-imino rhodium(II) carbenoid, leading to a transient 1-imino-2-vinylcyclopr

147 rom the transient N,O-dilithiated hemiaminal carbenoids leads to the formation of singlet carbenes fo

148 The scrambling of halogens at the zinc carbenoid led to the formation of the fluorocyclopropana

149 ulfone with the more ionic lithium methylene carbenoids (LiCH2X, where X = Cl, Br, and I).

150 trisolvated monomer for the cis isomer and a carbenoid mechanism via disolvated monomer for the trans

151 eliminated via disolvated monomer through a carbenoid mechanism.

152 the theoretical calculations and the rhodium carbenoid mechanism.

153 A novel carbenoid-mediated approach to thioisomunchnones was dev

154 A zinc carbenoid-mediated chain extension of a beta-dicarbonyl

155 The application of a zinc carbenoid-mediated chain-extension reaction to a functio

156 nzyme/cofactor pair is active in non-natural carbenoid-mediated olefin cyclopropanation.

157 nsaturated-gamma-keto lactone through a zinc carbenoid-mediated reaction.

158 idly assembled through an unprecedented zinc carbenoid-mediated tandem chain extension-acylation reac

159 genic centers, by employing the N-O tethered carbenoid methodology.

160 fford 6 but with the added twist that the Li-carbenoid moiety stays intact and does not transmetalate

161 The alkyl-substituted carbenoid n-BuCHBrLi reacts > or = 40 times more slowly

162 A concerted or nearly concerted metal carbenoid N-H insertion reaction mechanism is proposed.

163 ta-oxodithioesters with in situ generated Cu-carbenoids of diazocarbonyls.

164 syntheses, the eliminative cross-coupling of carbenoids offers a connective approach to olefins capab

165 rocyclization of a chlorovinylidene chromium carbenoid onto a pendant aldehyde to generate the C8-C9

166 on involves addition of a rhodium-stabilized carbenoid onto the acetylenic pi-bond to generate a cycl

167 proceeds by addition of a rhodium-stabilized carbenoid onto the acetylenic pi-bond to give a vinyl ca

168 involves cyclization of the initially formed carbenoid onto the alkyne to produce a butenolide which

169 le by intramolecular cyclization of the keto carbenoid onto the oxygen atom of the neighboring keto g

170 ne promotes indole modification with rhodium carbenoids over a broad pH range (2-7).

171 , whereas certain carbophilic metals trigger carbenoid/oxonium type pathway.

172 actions represent the full spectrum of known carbenoid pathways to cyclopropanation.

173 of the relatively inaccessible and expensive carbenoid precursor fluorodiiodomethane.

174 The carbenoid precursor is prepared via a 3-step sequence fr

175 tilizes 4-aryl-1-sulfonyl-1,2,3-triazoles as carbenoid precursors and the rhodium(II)-tetracarboxylat

176 hane and ethylzinc iodide as the substituted carbenoid precursors.

177 C-H functionalization of indoles via Fe carbenoids presents an attractive strategy to obtain bio

178 hodium-catalyzed reactions of donor/acceptor carbenoids proceeding by means of zwitterionic intermedi

179 echanism by which cyclopropyl and vinylidene carbenoids react with nucleophiles.

180 he first computational investigations of the carbenoid reactions of alpha-lithiated dimethyl ether (m

181 remaining products are formed primarily via carbenoid reactions that are enumerated.

182 istent with a change in the structure of the carbenoid reagent during the course of the reaction.

183 these silyl vinylketenes to participate with carbenoid reagents in [4 + 1] annulation reactions was i

184 Carbenoid ring opening is similar to the process predict

185 While the sodium and potassium chloride carbenoids showed high stabilities independent of the so

186 While the sodium and potassium chloride carbenoids showed high stabilities independent of the so

187 as prepared via a Rh(II)- or Cu(I)-catalyzed carbenoid Si-H insertion, was used to introduce the desi

188 tereochemical configurations of the reacting carbenoid species are defined.

189 posed to involve the formation of a cationic carbenoid species bearing structural resemblance to the

190 ation function (ELF) characterizes DFAY as a carbenoid species participating in cb-type 32CA reaction

191 mputational studies based on the proposed Au carbenoid species provide insight into this unique selec

192 -lithio dianion (PhCLiCN)(-)Li(+) leads to a carbenoid species, the C-lithio monoalkylated nitrile Ph

193 ermediate, possibly a zwitterionic palladium carbenoid species.

194 ain the pronounced solvent dependency of the carbenoid stability.

195 by the selenocysteine ligation, with rhodium carbenoids, stabilized and unstabilized, enables the att

196 The carbenoid stereochemical pairing [i.e., "like"=(S)+(S) o

197 species, but not a radical anion or radical-carbenoid structure.

198 ity is the use of donor/acceptor-substituted carbenoids such as those derived from methyl aryldiazoac

199 f the simplest azomethine ylide to that of a carbenoid TAC participating in cb-type 32CA reactions to

200 found for transformations of donor/acceptor carbenoids than for those of acceptor systems, primarily

201 e (Cu(II)hfacac(2)) to form a putative metal carbenoid that gives a productive dearomative reaction w

202 onto the acetylenic pi-bond to give a vinyl carbenoid that subsequently cyclizes onto the neighborin

203 first general intermolecular reactions of Rh-carbenoids that are selective over tertiary beta-C-H bon

204 -mediated cyclization to afford isoindazolyl carbenoids that could be trapped with 2,3-dimethyl-2-but

205 metallation occurs from both Fe to Cu and Li-carbenoid to Cu, resulting in the trimetallic Cu cluster

206 Predissociation of the carbenoid to cyclopropylidene + LiBr is not supported by

207 100% regioselective addition of the rhodium carbenoid to endocyclic nitrogen atom of the 2H-azirine-

208 mary boronic ester with a butenyl metallated carbenoid to generate a 1,3-bis(boronic ester).

209 chemoselective addition of halomethyllithium carbenoids to Weinreb amides at -78 degrees C.

210 6 is subsequently treated with CuCl, the Li-carbenoid transmetalates to Cu, which allows the control

211 The carbenoid-type (cb-type) 32CA reaction of 1,1-difluoroat

212 The resultant carbenoids underwent facile cyclization onto the neighbo

213 The cyclized carbenoid was found to undergo both aromatic and aliphat

214 Formal aromatic C-H insertion of rhodium(II) carbenoid was intensively investigated to develop a new

215 ties independent of the solvent, the lithium carbenoid was stable at room temperature in THF but deco

216 ties independent of the solvent, the lithium carbenoid was stable at room temperature in THF but deco

217 ropanes with metals or alkyllithiums affords carbenoids which undergo low-temperature ring opening to

218 The use of lithium carbenoids, which are less sensitive to steric hindrance

219 rbohydrate and the phenyl group of the metal carbenoid, while pai/pai interactions with the C2-OBn su

220 iants generated from the interaction of a Rh-carbenoid with an allene have been applied to the synthe

221 ion occurs through cycloaddition of a copper carbenoid with an ester, followed by a Lewis acid-cataly

222 for reaction of a phenyl-substituted rhodium carbenoid with styrene match within the error of the exp

223 and rearrangements by trapping of the metal carbenoids with a diverse range of coupling partners (e.

224 g, etc.) to generate the corresponding metal carbenoids with extrusion of nitrogen.

225 The homologation of phosphorus carbenoids with organoboranes leads to alpha-boranophosp

226 Herein, we report a new class of stable carbenoids with sulfinate as nucleofuge for Matteson-typ

227 resulting from a Wolff rearrangement of the carbenoid, with a rhodium peroxide or peroxy radical spe

228 edict modestly exergonic dimerization of the carbenoid, with or without solvation, and the dimer appe

229 nc carbenoid IZnCH2I relative to dialkylzinc carbenoid Zn(CH2I)2, which is responsible for the initia