ライフサイエンスコーパス: carborane

1 bsorbing [cyanine(+)] with the inertness of [carborane(-)].

2 y be due to the porphyrin, not the borane or carborane.

3 formally viewed as a deprotonated hypercloso carborane.

4 roved the need for eight hydroxyl groups per carborane.

5 ertices (B(2), B(4), B(5), and B(9)) of meta-carborane.

6 , boron-rich pincer complexes derived from m-carborane.

7 reactions of carbenes into cage B-H bond of carboranes.

8 ctron-rich and electron-poor B-H vertices in carboranes.

9 inishes with the formation of hexyl or butyl carboranes.

10 to produce the 6-(RR'N)- nido-5,7-C 2B 8H 11 carboranes.

11 Carborane 1 has been easily converted to its lithium and

12 -C) "negative hyperconjugation" in diamino-o-carborane (1) causes rapid inversion in the amine, which

13 ubstituted p-carboranes via triphenylsilyl-p-carborane (1).

14 ing properties of an ortho-substituted closo-carborane (1,2-(Ph(2)PO)(2)-1,2-C(2)B(10)H(10)) cluster

15 c 6- and 12-vertex closo ortho-carboranes (o-carboranes) 1,2-R2-1,2-C2BnHn (R = H, CH3, NH2, OH, F, S

16 s the terminal N-mu(2) -bridged zwitterionic carborane-1,2-bis(silylium) AdN(3) adduct 2 with an open

17 (2) formed closo-1,12-bis(lithiosulfinato)-p-carborane (10) in nearly quantitative yield.

18 ding 1,12-bis(sulfonic acid) derivative of p-carborane (12) was obtained in high yield by treating 10

19 converted to closo-1,12-bis(sulfinic acid)-p-carborane (13) via H(+)-exchange.

20 oduct, closo-B-decahydroxy-1-sulfonic acid-p-carborane (14) was formed.

21 rded B-decahydroxy-1,12-bis(sulfonic acid)-p-carborane (15) in 40% yield.

22 ly in 88% yield by heating 1-sulfinic acid-p-carborane (17) in H(2)O(2) (30%).

23 11, and 1.807 angstrom for 1b (amino oxide-o-carborane), 1i (di-N,N-dimethylamino-o-carborane), and 2

24 The less toxic nido-carborane 2 was also tested as a candidate for boron neu

25 o-B-decamethoxy-1,12-bis(methyl sulfonate)-p-carborane (20).

26 Cubane (19) and closo-carborane (23) analogues exhibited improved in vitro pot

27 ivity was modest, with one sample, the closo-carborane 4, showing about 10-fold greater activity.

28 undergoes deboronation to yield anionic nido-carborane, a poor guest for CB[7], facilitating recovery

29 ated on the basis of the covalently attached carborane, a recently introduced grafted calcium ionopho

30 serve as electronic analogs of neutral closo-carboranes, achieving similar electronic directing effec

31 The carborane acid H(CHB(11)Cl(11)) reacts with chloroalkane

32 by the strongest known solid superacid, the carborane acid H(CHB(11)Cl(11)), has been studied by qua

33 The hydrated carborane acid H(CHB(11)I(11)).8H(2)O crystallizes in na

34 The carborane acid H(CHB11F11) is therefore the strongest kn

35 erization take place in the presence of free carborane acid that finishes with the formation of hexyl

36 The strongest carborane acid, H(CHB11F11), protonates CO2 while tradit

37 1)) that accounts for the greater acidity of carborane acids.

38 of a (10)B-enriched polyhedral borane and a carborane against mouse mammary adenocarcinoma solid tum

39 gioselectivity and ease of derivatization of carboranes allows for facile syntheses of a wide variety

40 d three-cage oligomers containing both ortho-carborane and dodecaborane moieties.

41 The electron withdrawing effect of ortho-carborane and lack of pi-delocalization of the LUMO rati

42 zed by kinetic protection by the chlorinated carborane and the delocalization of spin density through

43 yses, visually reveal the region between the carborane and the phthalimide ligands responsible for th

44 stitution reactions on the boron vertices of carboranes and boranes is noted.

45 tions of racemic mixtures of anionic cluster carboranes and metallacarboranes that represent an analy

46 However, only two families-carboranes and polyhedral oligomeric silsesquioxanes (PO

47 the chemical stability/lipophilicity of the carboranes and tetrakis[3,5-bis(trifluoromethyl)phenyl]

48 expansion of research in the field of stable carboranes and their wide potential in the drug design r

49 ide-o-carborane), 1i (di-N,N-dimethylamino-o-carborane), and 2g (di-N,N-diisopropylamino-o-dodecahedr

50 o samples such as boron carbide, boric acid, carborane, and borosilicate glass.

51 Icosahedral boranes, carboranes, and metallacarboranes are extraordinarily ro

52 Cluster carboranes, and possibly other heteroboranes, thus appea

53 The combination of nido-carborane- and FESAN-linked nucleotides with 7-ferroceny

54 The nido-carborane- and FESAN-modified nucleotides gave analytica

55 the silver(I) salt of the highly methylated carborane anion [closo-1-H-CB(11)Me(11)](-) is described

56 ers from standard l-PIB in that it carries a carborane anion attached at the chain end.

57 to evaluate the ion-pairing ability of each carborane anion in situ (i.e., within bis(2-ethylhexyl)

58 he redox properties of a triazole fused to a carborane anion through methylation to form a zwitterion

59 the chemical stability of the perhalogenated carborane anion to that of the best lipophilic tetraphen

60 te base is the exceptionally inert CB11H6X6- carborane anion, separates Bronsted acidity from oxidizi

61 2 halide positions of the CB(11) icosahedral carborane anion.

62 stretching frequency on the basicity of the carborane anion.

63 ation equivalents partnered with halogenated carborane anions (such as Et(3)Si[HCB(11)H(5)Cl(6)]) fun

64 Mes)3Si+ cations are well separated from the carborane anions and benzene solvate molecules.

65 Polyhalogenated closo-12-vertex carborane anions are thought to be inert species incapab

66 has been developed using weakly nucleophilic carborane anions as leaving groups.

67 inated tetraphenylborate counterions because carborane anions can sustain much higher levels of acidi

68 Five CHB(11)X(6)Y(5)(-) carborane anions from the series X = Br, Cl, I and Y = H

69 s in the solid state, arising from proximate carborane anions in the crystal lattice.

70 Large, inert, weakly basic carborane anions of the icosahedral type CHB(11)R(5)X(6)

71 cation scales linearly with the basicity of carborane anions on the nuNH scale.

72 abrominated (HBC), and undecaiodinated (UIC) carborane anions were prepared and evaluated for their p

73 When partnered with carborane anions, arenium ions are remarkably stable.

74 Inert weakly coordinating carborane anions, CB(11)H(6)X(6)(-) (X = Cl, Br), allow

75 Classically closo-carborane anions, particularly [HCB(11)H(11)](-) and [HC

76 ments supported the covalent grafting of the carborane anions.

77 F(15)Tr(+)) in combination with halogenated carborane anions.

78 s, namely N-heterocyclic carbenes (NHCs) and carborane anions.

79 meter tubes of H(aq)(+) enclosed by walls of carborane anions.

80 The carborane-appended pi-conjugated compounds are found to

81 t is widely accepted that closo-boranes and -carboranes are aromatic compounds.

82 Carboranes are boron-rich molecules that can be function

83 m- and p-Carboranes are compared with m- and p-phenylenes as conj

84 - and two-electron reduced forms of diaryl-o-carboranes are disclosed to gain insight into their well

85 o boranes, [B(n)H(n)](2-) (5 <= n <= 14) and carboranes are examples of compounds that are singly 3D-

86 ontact ion pairs of the type [H(3)O(+).nSolv.Carborane] are formed and close to C(3v) symmetry is ret

87 is work, we elucidate the potential of ortho-carborane as an AIE-active component in the design of NI

88 ups at the B(2) vertex using B(9)-bromo-meta-carborane as the sole starting material through substrat

89 the exploitation of the unique properties of carboranes as potent and selective pharmacophores.

90 e derivatives bearing three, four, and six p-carboranes as potential wheels attached to a semirigid c

91 Here, we present polyhedral boron clusters (carboranes) as strongly binding, yet easily removable, g

92 licity of silylium ion-like species, Et(3)Si(carborane), as the driving force to obtain increased alk

93 report the synthesis and characterization of carborane-based 1,8-naphthyridinones and thiazoles as no

94 work, we demonstrate novel phenyl borate and carborane-based anions paired with a near-infrared (NIR)

95 A novel carborane-based electrolyte incorporating an unprecedent

96 ecently, we developed OSU-ERbeta-12, a novel carborane-based ERbeta agonist that has a greater than 1

97 using a trinuclear Hg(II) complex containing carborane-based ligands, [9]-mercuracarborand-3, or MC3

98 he first demonstration of self-assembly of a carborane-based molecule in the absence of metals.

99 B agonists and support further evaluation of carborane-based selective estrogen receptor modulators.

100 Fs), NU-2004 and NU-2005, by incorporating a carborane-based three-dimensional (3D) linker and using

101 determined, revealing covalence in the alkyl-carborane bonding.

102 g moieties, we describe here how icosahedral carboranes-boron-rich clusters-can influence metal-ligan

103 zed HCl elimination reaction to form a butyl carborane, Bu(CHB(11)Cl(11)), beginning an oligomerizati

104 These assemblies incorporate carborane building blocks and were prepared in excellent

105 ggest the utilization of bis-deoxygalactosyl-carborane building blocks in solid phase peptide synthes

106 introduction of multiple bis-deoxygalactosyl-carborane building blocks to the GRPR-selective ligand [

107 The X-ray structures of two linear carborane building blocks, 1,12-(4-CC(C(5)H(4)N)(2)-p-C(

108 ppressed by using l-deoxygalactosyl modified carborane building blocks.

109 hesized from diphenylmethylsilyl-protected p-carborane by using the method employed in the synthesis

110 Icosahedral carboranes, C(2)B(10)H(12), have long been considered to

111 monstrates the successful incorporation of a carborane cage as an internal counteranion bridging betw

112 espectively), depending on which atom of the carborane cage is attached to the thioether moiety.

113 f the motion is intramolecular rotation of a carborane cage ligand (7,8-dicarbollide) around a nickel

114 f incubation, whereas nido-OPDs in which the carborane cage was located along the oligomeric backbone

115 However, nido-OPDs in which the carborane cage was located on a side chain attached to t

116 a sequential loss of methyl groups from the carborane cage with a transient formation of similar bor

117 sting electronic properties imposed by the m-carborane cage.

118 gly reduced, protonated form of the diaryl-o-carborane can mediate multi-ET/PT reductions of azoarene

119 by computational work, show that icosahedral carboranes can act either as strong electron-withdrawing

120 Accordingly, carboranes can be efficiently installed on proteins by e

121 , they are much higher if a more hydrophilic carborane cation-exchanger is incorporated in the membra

122 work revisits the Wade-Mingos (W-M) rules in carborane chemistry by showing that substituent effects,

123 We have combined carborane chemistry with the newly developed directional

124 two frontier orbitals exists in the bridging carborane cluster.

125 the donor and acceptor substituents via the carborane cluster.

126 phosphine centers and the electron-accepting carborane cluster.

127 njugated compounds containing three to six o-carborane clusters have been synthesized by employing pa

128 Incorporation of o-carborane clusters into extended pi-conjugated systems l

129 Decapitation of o-carborane clusters made these extended trimers water sol

130 inimal ion loss using isotopologues of three carborane compounds ranging in m/z from 320 to 1020.

131 cles, yielding the corresponding substituted carboranes containing B-O, B-S, B-Se, B-Te, and B-C bond

132 e, we report the synthesis and evaluation of carborane-containing analogs of the promising NSAID phar

133 Carborane-containing extended trimers were found to emit

134 nd N) bond formation for the installation of carborane-containing moieties onto small molecules and p

135 g to a PT/ET/PT mechanism, where the reduced carborane core is itself highly stable to protonation.

136 O)n(+) cations for n = 3-8 with weakly basic carborane counterions has been studied by IR spectroscop

137 This is made possible by using carborane counterions of the type CHB(11)R(5)X(6)(-) (R

138 dines in 2-ethoxyethanol results in a facile carborane deboronation and the formation of robust and h

139 taining (10)B-enriched polyhedral borane and carborane derivatives for the treatment of head and neck

140 racteristics of easily accessible borane and carborane derivatives, which are excellent materials for

141 The m- and p-carborane dicarboxylates were utilized as the donor link

142 ) complexes have been prepared with the nido-carborane diphosphine.

143 rization ("cage-walking") of B(9)-bromo-meta-carborane during Pd-catalyzed cross-coupling, which enab

144 tylide complexes featuring 10- and 12-vertex carboranes embedded within the diethynyl bridging ligand

145 The pharmacological properties of our para-carborane ERB selective agonists measure favorably again

146 We synthesized a series of para-carborane estrogen receptor agonists revealing an ERB se

147 y eliminates HCl (but not DCl) to form ethyl carborane, Et(CHB(11)Cl(11)), which binds a second molec

148 ontrast to carbon-based ligands, icosahedral carboranes exhibit a significant dichotomy in their coor

149 Two-electron reduction of 1,1'-bis(o-carborane) followed by reaction with [Ru(eta-mes)Cl2 ]2

150 a C-N-C mode in which the bulky and rigid o-carborane fragment is cyclometalated via a C atom.

151 he absorption and fluorescence data for both carboranes from experimental techniques (including femto

152 ution of the thiol proton in cysteine with m-carborane furnished 2-amino-3-(1,7-dicarba-closo-dodecac

153 r chelating ligands featuring meta- or ortho-carboranes grafted on the sulfur atom, we were able to t

154 s to overcome the high hydrophobicity of the carborane group and enable chemoselective conjugation of

155 s of seven BODIPYs functionalized with ortho-carborane groups at the 8(meso) or 3/5(alpha) position w

156 uencies decrease in the order fluoroanions > carboranes > oxyanions, reflecting the relative basiciti

157 e showcase the utility of the modified ortho-carborane guest by recycling a CB[7]-functionalized resi

158 While the neutral carboranes have been widely investigated for this purpos

159 Salts of the type [H(arene)][carborane] have been prepared by protonating benzene, to

160 oved with fluoride to give monosubstituted p-carboranes I, which upon further nucleophilic substituti

161 Functionalization of carboranes, icosahedral boron-carbon molecular clusters,

162 on further nucleophilic substitution yield p-carboranes II.

163 By incorporating ortho-carborane in the backbone of a conjugated polymer, a rem

164 Icosahedral carboranes in medicine are still an emerging class of co

165 r the first time, we report the use of bromo-carboranes in palladium-catalyzed cross-coupling for eff

166 n-stereocenter adjacent to cage boron of the carborane, in excellent site- and enantioselectivity und

167 exhibit close pi-pi pyridine and pyridine-B(carborane) interactions, which are discussed.

168 ysis of the closo-1,12-bis(chlorosulfonyl)-p-carborane intermediate.

169 lize these trends, we classified the studied carboranes into 28 domains defined by CAEN environments.

170 ver, few general approaches to readily embed carboranes into small molecules, peptides, and proteins

171 which the boron atom in position 9 or 10 of carborane is attached to a positively charged sulfur ato

172 ease in the ligand bite angle when the closo-carborane is reduced to the nido-carborane, resulting in

173 e aromaticity observed in closo-boranes and -carboranes is also present in their nido counterparts, a

174 of such an approach a class of C,C'-diaryl-o-carboranes is herein explored as a conceptual substitute

175 arge transfer (LML'CT) transitions from nido-carborane ligand (L) to metal/ligand group "gold(I)-NHC

176 ilized by the chelating bis(silylenyl)-ortho-carborane ligand, 1,2-(LSi)(2)-1,2-C(2)B(10)H(10) [L = P

177 Two boron-containing, ortho-icosahedral carborane lipophilic antifolates were synthesized, and t

178 pi-interactions associated with hydrophobic carboranes may be exploited to enhance the selectivity o

179 approach enables the rapid incorporation of carborane moieties into small molecules, peptides, and p

180 cement of a phenyl ring in the NSAIDs with a carborane moiety greatly decreases their COX activity wi

181 Thus, the introduction of a carborane moiety is an appropriate tool for modifying li

182 ppeared that a closer proximity of the bulky carborane moiety to the nucleoside scaffold resulted in

183 ing affinity of known CB(2)R radioligands, a carborane moiety was used as a bioisostere.

184 The unusual reactivity of carborane mono- and dialdehydes with pyrroles in the pre

185 ially dianionic 6- and 12-vertex closo ortho-carboranes (o-carboranes) 1,2-R2-1,2-C2BnHn (R = H, CH3,

186 The first C-bound ortho-carborane (oCb) supported hypervalent iodine(III) -IL(2)

187 al dialkylchloronium ions decompose to alkyl carboranes of formula Bu(C(2)H(4))(n)(CHB(11)Cl(11)) up

188 In many cases bromo-carboranes outperform the traditionally utilized iodo-ca

189 The featured o-carborane (PhCbPh(N)) can be reduced and protonated to g

190 This reaction thereby generates carboranes possessing a carbon-stereocenter adjacent to

191 racterize the cellular uptake of the cyanine-carborane PSs, organelle localization, generation of rea

192 Upon basic treatment, ortho-carborane readily undergoes deboronation to yield anioni

193 Carboranes represent a class of compounds with increasin

194 Carboranes represent a potentially rich but underutilize

195 hus, site- and enantioselective synthesis of carboranes requires complete control of the reaction.

196 -C(2)B(7)H(13) and arachno-4,6-C(2)B(7)H(13) carboranes, respectively.

197 n the closo-carborane is reduced to the nido-carborane, resulting in C-C bond rupture and cage openin

198 d to the remarkably stable tert-butyl cation carborane salt.

199 These newly developed [cyanine(+)] [carborane(-)] salt PSs introduce a potent therapeutic ap

200 Here, we report the discovery of cyanine-carborane salts as potent photosensitizers (PSs) that ha

201 The implementation of [cyanine(+)] [carborane(-)] salts dramatically enhance cancer targetin

202 h tertiary alkyl centers, as in [tert-butyl][carborane] salts.

203 Carborane scaffolds offer many unique advantages includi

204 These and similar results with carborane-selenol derivatives suggest that, in contrast

205 s outperform the traditionally utilized iodo-carborane species.

206 It is suggested that the efficacy of the p-carborane stopper is reduced by the presence of the two

207 es but to the location of the C atoms in the carborane structure.

208 ect electrophilic insertion, promoted by the carborane substituent in the 13-vertex/12-vertex precurs

209 and the corresponding neutral NH(2)-closo-m-carborane-substituted counterparts.

210 aluation of the zwitterionic NH(3)(+)-nido-m-carborane-substituted Thds indicated improved aqueous so

211 ry includes six zwitterionic NH(3)(+)-nido-m-carborane-substituted thymidine analogues (Thds) and the

212 MR experimental spectra of boron-iodinated o-carboranes suggest that these two oxidized forms of a cl

213 , mesitylene, and hexamethylbenzene with the carborane superacid H(CB(11)HR(5)X(6)) (R = H, Me; X = C

214 The carborane superacid H(CHB11 F11 ) is that acid.

215 We report a class of carborane-supported, highly electrophilic silylium compo

216 From quantum chemical calculations on these carborane systems, the charge transfer process depends o

217 prepared boron-functionalized 9-amino-ortho-carborane that binds to CB[7] with a K(a) ~ 10(10) M(-1)

218 rophores, such as BODIPY for imaging, and in carboranes that are potential neutron capture therapy ag

219 bollide ions are an intriguing class of nido-carboranes that mimic the behavior of the cyclopentadien

220 istical, but with recovery of the starting p-carborane, the effective conversion to 1 is about 90%.

221 Herein we report the use of carboranes to significantly increase the potency of smal

222 y and suitable electrostatic properties, the carboranes, UIC in particular, are a very promising alte

223 coordinating SbF6(-) and weakly coordinating carborane [undecamethylcarborane HCB11Me11(-) (CB(-))],

224 itrogen or boron atoms, e.g., C(2)B(10)H(12) carboranes versus planar N(2)C(4)H(4) diazines or [B(2)C

225 ane-1-carboxylic acid was synthesized from p-carborane via 1 in 62% overall yield, a considerable imp

226 ry in the synthesis of heterodisubstituted p-carboranes via triphenylsilyl-p-carborane (1).

227 A maximized number of carboranes was introduced to the hY(1)R-preferring ligan

228 u(CO)2 (POBBOP = 1,7-OP(i-Pr)2-2,6-dehydro-m-carborane) was synthesized by double B-H activation with

229 tituted and asymmetric B(9)-substituted nido-carboranes were studied.

230 e arrangement of their molecular axles and p-carborane wheels relative to the chassis would be conduc

231 typically associated with icosahedral closo-carboranes, where a carbon-based vertex induces a strong

232 We compare the inclusion of carborane with other similarly sized substituents and de

233 The reactions of the arachno-4,6-C 2B 7H 13 carborane with the secondary and primary amines, Me 2NHB

234 oluble S-substituted charge-compensated nido-carboranes with free functional groups were prepared.

235 te the difficulty in the deboronation of the carboranes with their stability and aromaticity.

236 -dicarbadodecaborane(12) (1,12-bis(lithio)-p-carborane) with SO(2) formed closo-1,12-bis(lithiosulfin