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 on reaction with a tertiary amine containing carbenoid.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

38 Two carbenoids combine to generate an olefin by a mechanism

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

62 The carbenoid geometries are dependent on the heteroatom and

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

87 electrophilicity between the various rhodium carbenoid intermediates.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

106 the theoretical calculations and the rhodium carbenoid mechanism.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

125 of the relatively inaccessible and expensive carbenoid precursor fluorodiiodomethane.

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

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

128 hane and ethylzinc iodide as the substituted carbenoid precursors.

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

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

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

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

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

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

135 Carbenoid ring opening is similar to the process predict

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

137 tereochemical configurations of the reacting carbenoid species are defined.

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

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

140 ermediate, possibly a zwitterionic palladium carbenoid species.

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

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

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

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

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

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

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

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

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

150 100% regioselective addition of the rhodium carbenoid to endocyclic nitrogen atom of the 2H-azirine-

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

152 The resultant carbenoids underwent facile cyclization onto the neighbo

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

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

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

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

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

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

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

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

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

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