ライフサイエンスコーパス: carborane

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

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

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

4 formally viewed as a deprotonated hypercloso carborane.

5 inishes with the formation of hexyl or butyl carboranes.

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

7 Carborane 1 has been easily converted to its lithium and

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

34 Icosahedral boranes, carboranes, and metallacarboranes are extraordinarily ro

35 Cluster carboranes, and possibly other heteroboranes, thus appea

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

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

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

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

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

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

42 2 halide positions of the CB(11) icosahedral carborane anion.

43 stretching frequency on the basicity of the carborane anion.

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

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

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

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

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

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

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

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

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

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

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

55 ments supported the covalent grafting of the carborane anions.

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

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

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

59 Carboranes are boron-rich molecules that can be function

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

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

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

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

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

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

66 A novel carborane-based electrolyte incorporating an unprecedent

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

83 We have combined carborane chemistry with the newly developed directional

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

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

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

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

88 Carborane-containing extended trimers were found to emit

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

109 on further nucleophilic substitution yield p-carboranes II.

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

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

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

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

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

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

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

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

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

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

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

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

122 Carboranes represent a potentially rich but underutilize

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

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

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

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

127 s outperform the traditionally utilized iodo-carborane species.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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