ライフサイエンスコーパス: geminal

1 rrelates with a conformational dependence of geminal 119Sn-15N couplings and a possible correlation w

2 l pathway where isocyanides acted as radical geminal acceptors generating key imidoyl radical species

3 f tetrasubstituted allenes featuring a novel geminal acyl/alkoxy substitution.

4 t the 3 degrees ROH is not possible, and the geminal alkyl groups could sterically shield the OH grou

5 SiMe3)2, are active for the hydrogenation of geminal and 1,2-disubstituted alkenes.

6 cal 1,2- and 1,4-boron migrations to provide geminal and 1,3-bisborylalkanes are efficient transforma

7 effect on acyclic conformation, inducing the geminal and vicinal hydrogens on the adjacent sp3-sp3 C-

8 In vacuo and solvated DFT calculations of geminal and vicinal J(CH) and J(CC) values are similar a

9 ired electrons of Bt being stabilized by the geminal anionic oxygen.

10 istic experiments with chiral (10)B-enriched geminal bis(boronates) suggest that the reaction occurs

11 eneous catalysis, especially those involving geminal bis(pinacolatoboronates) and 1,4-azaborines, are

12 c-group-selective cross-couplings of achiral geminal bis(pinacolboronates) provide a route for the co

13 ation, followed by C-H borylation to provide geminal bis-borylated products.

14 rates, providing high yield of the mono- and geminal bis-borylation products.

15 between the structures of a wide variety of geminal bisphosphonates and their activity in inhibiting

16 while the other is charged, and finally the geminal bisylides, for which the two substituents are po

17 Geminal bromofluoroalkenes are an important subclass of

18 ereoselective synthesis remained elusive for geminal bromofluoroalkenes before our work.

19 selective substrates are those containing a geminal bulky substituent on the enoxysilane.

20 ersible steps ii and iii, and interchange of geminal C H bonds of the methane and cyclohexane C H sig

21 mines, or (chiral) gamma-lactams through two geminal C-C bond or two C-N bond formations, respectivel

22 ing C-F bonds to be exceptionally strong and geminal C-F bonds to strengthen one another(4).

23 demonstrate the first example of a directed, geminal C-H bisoxidation, a new fragmentation cascade to

24 additional Rh(I)...H-C interactions with the geminal C-H bonds are also evident.

25 The lack of a hydroxyl group on the geminal carbon also reduced K(isom).

26 central bond, whereas bisubstitution on the geminal carbon leads to a shortening of this bond due to

27 logue show intrinsic isotope shifts from the geminal CD(3) and from only one distant CD(3), an unusua

28 ine-N-oxides) with hydrochloric acid affords geminal chloronitroso compounds bearing a distant hydrox

29 become involved in NCHBs, they polarize the geminal -CHX- hydrogen at the pseudoanomeric position to

30 f the catalytic mechanism, followed by their geminal coupling with O atoms coordinated by the same Co

31 These geminal couplings depend highly on the orientation of C-

32 Existing methods require deborylation of geminal di-/triboryl alkanes and/or the presence of addi

33 olution (DKR) protocols were developed using geminal diacetate as an acylating agent, resulting in ch

34 Geminal diacetates have been used as sustainable acyl do

35 Moreover, it was shown that acylation using geminal diacetates resulted in remarkable regioselectivi

36 Especially, it was revealed that geminal diacetates showed higher reactivity than vinyl a

37 2-Amino-4H-pyrans undergo geminal dialkoxylation with the migration of an amino gr

38 The rates for the formation of the geminal diamine and external aldimine in this pathway we

39 he PLP group that accompany formation of the geminal diamine complex, the first intermediate in the r

40 phosphates appear to be primarily present as geminal diamine complexes, with bonds to both glycine an

41 e excitation and emission wavelengths of the geminal diamine intermediate, we were able to monitor th

42 tor the formation and decay of two different geminal diamine species.

43 Finally, the formation of the geminal diamine was determined to be Mg2+-dependent.

44 The electron density reveals that the geminal diamine, a tetrahedral intermediate in the forma

45 rapid equilibrium of isomeric aldimines and geminal diamines.

46 e syntheses and electronic structures of the geminal dianions are presented, followed by the studies

47 r two lone pairs at the same C center, i.e., geminal dianions, stabilized by main group elements.

48 ric induction in the desymmetrization of the geminal diaryl motif, located on a carbon or phosphorus

49 Geminal diazides constitute a rare class of compounds wh

50 The degradation of geminal diazides is described.

51 A broad range of geminal diazides with various structural motifs includin

52 n aqueous DMSO providing a general access to geminal diazides.

53 rminal triple bond with the formation of the geminal diborane followed by ring closure via intramolec

54 A geminal diboron system ensures site-, regio-, and diaste

55 Geminal diboronates have attracted significant attention

56 lease induced 1,2-metallate rearrangement on geminal diborons and Ir catalyzed multicomponent allylat

57 The development of geminal diborons as soft pronucleophiles also enabled th

58 We present a strategy to engage non-terminal geminal diborons in 1,2-boronate shift via ring-opening

59 rated via deprotonation of the corresponding geminal diborons.

60 1,2-metallate rearrangement of geminal diboryl alkanes typically requires an alpha-leav

61 termediate in many chemistries, forms stable geminal dicarbonyl Rh complexes (Rh(+)(CO)(2)), that cou

62 amonolayer coverages (CO*/Ru > 1) by forming geminal dicarbonyls at low-coordination corner/edge atom

63 The requisite allylic geminal dicarboxylates are prepared in good yields and h

64 Asymmetric alkylations of allylic geminal dicarboxylates with dialkyl malonates have been

65 The solvation properties of the geminal dicationic ILs tend to be similar to those of th

66 Thirty-nine geminal dicationic ILs were synthesized and characterize

67 more highly cross-linked stationary phase of geminal dicationic ILs, exclusively, an increase in effi

68 rmination of water due to the new PEG-linked geminal dicationic ionic-liquid-coated GC capillary colu

69 degrees C for one of the pyrrolidinium-based geminal dicationic liquids.

70 Here, we leverage phosphonium-based geminal dications to control interfacial cation arrangem

71 The various geminal dications were paired with up to four different

72 ploying the readily available and economical geminal dichloroimidazolidinediones (DCIDs) that promote

73 Geminal dichloromethane functionality was introduced by

74 was used to investigate the role of the 3,3-geminal diester groups and the origin of torquoselectivi

75 hod for the catalytic, asymmetric, migratory geminal difluorination of beta-substituted styrenes to a

76 Structural modification by changing the geminal difluoro group in PT2385 to a vicinal difluoro g

77 [GEM] was also computed to determine how the geminal difluoro group of dFdC perturbs DNA electrostati

78 ased electron density in the vicinity of the geminal difluoro group.

79 lytic asymmetric cross-coupling that employs geminal dihalides as electrophiles.

80 The reaction of geminal dihalocyclopropanes with metals or alkyllithiums

81 A chemoselective, tandem geminal dihalogenation of an unactivated methyl group, a

82 hemical stability of molecules incorporating geminal diheteroatomic motifs can be modulated by physic

83 In this Perspective, we exemplify geminal diheteroatomic motifs that have been utilized in

84 ilyldiperoxyketals and -acetals derived from geminal dihydroperoxides and from a new method employing

85 substituted hexofuranoses 7a-c with required geminal dihydroxymethyl group.

86 Three cases can thus be considered: the geminal-dilithio derivative, for which the two substitue

87 of DMDO is largely a consequence of combined geminal dimethyl and dioxa substitution effects and its

88 ds to a dihydrodipyrrin-acetal (1) bearing a geminal dimethyl group and a p-tolyl substituent.

89 clic core by incorporation of a symmetrizing geminal dimethyl group at C5.

90 )N atoms yet lacks substituents other than a geminal dimethyl group in each pyrroline ring.

91 hydrogenation by virtue of the presence of a geminal dimethyl group in each pyrroline ring.

92 ded 3,13-substituted chlorins that contain a geminal dimethyl group in the pyrroline ring (for stabil

93 ation of a dihydrodipyrrin-acetal (bearing a geminal dimethyl group in the pyrroline ring) typically

94 se route to synthetic chlorins, which bear a geminal dimethyl group in the pyrroline ring, has been e

95 ns are sterically uncongested and bear (1) a geminal dimethyl group in the reduced pyrroline ring, (2

96 e been prepared wherein each chlorin bears a geminal dimethyl group in the reduced ring and a water-s

97 Chlorin building blocks incorporating a geminal dimethyl group in the reduced ring and synthetic

98 in is sterically uncongested and bears (1) a geminal dimethyl group in the reduced, pyrroline ring, (

99 o beta substituents, one meso substituent, a geminal dimethyl group to lock in the chlorin hydrogenat

100 chlorins that bear two meso substituents, a geminal dimethyl group to lock in the chlorin hydrogenat

101 The presence of the geminal dimethyl groups in 6SS increased the stability o

102 Each bacteriochlorin contains two geminal dimethyl groups to lock-in the bacteriochlorin h

103 d corrole, is enantiomeric, and contains two geminal dimethyl groups, 2,12-di-p-tolyl substituents, a

104 ring 4 position and additional substitution (geminal dimethyl or aryl) at the 5 position are crucial

105 ary C(sp(3))-H bonds in substrates that bear geminal dimethyl substituents furnished chiral amines th

106 MDO is largely a consequence of the combined geminal dimethyl- and dioxa-substitution effects and unu

107 Altering the geminal dimethylindoline core of the initial hit compoun

108 ic intermolecular arylation of disubstituted geminal dinitriles with in situ generated arylnickel com

109 the arylation of R-BINOL and S-BINOL derived geminal dinitriles, preserving optical purity.

110 dialdehydes yield on reaction with OH- ions geminal diol anion, which is electro-oxidized to a carbo

111 linked N2-(3-oxo-propyl)-dG aldehyde and its geminal diol hydrate.

112 statin B generates both a hemiaminal and a 3-geminal diol iminosugar (3-GDI) that are, rather than th

113 reactions of the C-7 methyl group to form a geminal diol intermediate, which spontaneously dehydrate

114 und I (Cmpd I) mediated deformylation of the geminal diol was considered in the context of the protei

115 designed to contain cleavable bonds such as geminal diol, disulfide, and acetal.

116 nediol [CH(2)(OH)(2)] transient-the simplest geminal diol-via energetic processing of low-temperature

117 to initiate a concerted deformylation of the geminal diol.

118 tually coupling the atmospheric chemistry of geminal diols and Criegee intermediates.

119 undamental chemistry and chemical bonding of geminal diols and signify their role as an efficient sin

120 t to water plus the aldehyde or ketone, free geminal diols represent one of the most elusive classes

121 Geminal diols-organic molecules carrying two hydroxyl gr

122 to a lesser extent ketones, hydrate to form geminal diols.

123 e prepared a new polymer which uses a pseudo-geminal disubstituted [2.2]paracyclophane scaffold to ho

124 for the catalytic hydroboration of terminal, geminal, disubstituted internal, tri- and tetrasubstitut

125 dation allows for the subsequent addition to geminal-disubstituted olefins regioselectively.

126 ts for the enantioselective hydrogenation of geminal-disubstituted olefins.

127 lene protons interfere with the reaction, so geminal disubstitution alpha to the amide carbonyl was n

128 Geminal disubstitution at the C(a) carbon in y(2,2) led

129 rovides a versatile and modular platform for geminal disubstitution of carbonyl oxygens.

130 Geminal disubstitution of cyclic monomers is an effectiv

131 and cellular antiviral data for a series of geminal disulfones.

132 derivatives to form hydrazido complexes and geminal double cleavage to form unusual late transition

133 , the highly diastereoselective synthesis of geminal E-bromofluoroalkenes was accomplished in one ste

134 ference compound is especially important for geminal electronegative substitutents.

135 ons between the geminal hydroxyl groups, the geminal fluorine atoms, and the active-site aspartate re

136 and octanitrocubane, and (8) the effects of geminal fluorine substitution at C-2 of 1,3-diradicals.

137 iplet states of diradical 6, which lacks the geminal fluorines at C-2 that are present in 4.

138 w that a cooperative interaction between the geminal fluorines at C2 and the fluorines at C1 and C3 i

139 the reason that addition of a second pair of geminal fluorines to methylenecyclopropane lowers the ba

140 hate; because of unusual interactions of the geminal fluorines, the ribose and base of GemdP shift su

141 thy synthesis (along with its monofluoro and geminal fluoro analogues).

142 Geminal frustrated Lewis pairs (FLPs) are expected to ex

143 transition metal-free, electrochemical sp(2) geminal functionalization of carbonyls enabled by anodic

144 mpounds 1b-d were compared with those of the geminal (gem) selectivity model ethyl tiglate (1a).

145 Geminal (gem-) disubstitution in heterocyclic monomers i

146 (2)H(1)]glucose have been used to assign the geminal H-6'a, H-6'b methylene bridge of the 11-carbon d

147 s and up to -109 Hz for (1)H-(1)H vectors of geminal hydrogen atoms (magnetic field of 14.09 T, tempe

148 magnetic environment in the capsule and the geminal hydrogen atoms of encapsulated alkanes show dias

149 nd bound in an unprecedented fashion via two geminal hydrogen atoms.

150 Charge analysis reveals that the geminal hydrogens are in fact more acidic than the agost

151 e shielding environment experienced by these geminal hydrogens differs by 1.26 ppm, indicative of pro

152 ymmetric pyrrolidine carbons and unsymmetric geminal hydrogens on the pyrrolidine ring, as confirmed

153 t symmetric, set of interactions between the geminal hydroxyl groups, the geminal fluorine atoms, and

154 e the dominant mechanism, sigma conjugation (geminal interactions) or sigma hyperconjugation (vicinal

155 udy, phlorins with different combinations of geminal methyl and phenyl substituents were prepared in

156 In BF dyes, the geminal methyl groups of carborhodamines are replaced wi

157 Changing the geminal methyl groups on 1alpha,25-dihydroxyvitamin D3 a

158 stereospecifically deuterated in one of the geminal methyl groups on C1 of the cyclohexene ring.

159 of a 23-yne function and replacement of the geminal methyl groups with trifluoromethyl groups, the o

160 sine, indicating that a positive charge on a geminal N does not inhibit the (1)H/(2)H exchange.

161 hydrogen whose bond is being cleaved but its geminal neighbor.

162 m for electronic structure where approximate geminal-occupation distributions are "learned" via a con

163 determination of the distribution of weights-geminal occupations-for general molecular systems has re

164 he presence of a 2-methyl substituent at the geminal or distal alpha-carbon, and (e) branching in the

165 Reaction of the geminal PAl ligand [Mes2PC( horizontal lineCHPh)AltBu2]

166 Using geminal phosphonium dications [C(n)(P(mmm))(2)][ClO(4)](

167 n-withdrawing fluoroaryl substituents in the geminal positions.

168 proton, thereby revealing coupling with the geminal proton.

169 Results indicate that the geminal protons of the A-ring, the H5 and H8 protons of

170 t topoisomerase II demonstrated that the H15 geminal protons of the etoposide A-ring, the H5 and H8 p

171 nsymmetric pyrrolidine carbons and symmetric geminal protons.

172 ine substituents are especially strain-rich: geminal, proximate, and W-related.

173 radical annulation using sulfur dioxide as a geminal radical acceptor/donor is presented.

174 in a variety of organic solvents, require a geminal relationship between a peroxyanion and a peroxid

175 The results suggest that geminal repulsion can provide a simple, unified explanat

176 In contrast, an explanation based on geminal repulsion provides a general conceptual framewor

177 based on 1,3 repulsive steric interactions (geminal repulsion) is proposed for explaining the variat

178 ered as the hidden face of their most famous geminal sibling, Polyproline II, as PPI is generally spo

179 ne is a good lone pair electron donor toward geminal sigma bonds.

180 Geminal sites ( identical withFe(OH2)2(+)) at this plane

181 The design relies on the incorporation of geminal substituents at C5 in combination with a substit

182 Importantly, geminal substituents on the trans-five-membered cyclic a

183 to the sterics of cis substituents, but not geminal substituents.

184 high, although in substrates not blocked by geminal substitution aromatization to a dipyrromethane i

185 yl-1,3-di-tert-butylbicyclo[1.1.0]butane and geminal substitution in 2,2'-di-tert-butylbicyclo[1.1.0]

186 lective, and the selectivity is increased by geminal substitution on carbon 3.

187 While beta-amino acids containing geminal substitution patterns have enormous potential fo

188 Geminal substitutions at different carbons along the bac

189 nhibitors, we have introduced a CF(2) moiety geminal to an amino group in the long tail of one of the

190 eprotonation of one of the C-H bonds that is geminal to the agostic interaction, rather than the agos

191 A key observation is that the hydrogen atoms geminal to the fluorine(s) become less positively charge

192 y the placement of various functional groups geminal to the H-C bond.

193 requiring only four general types of SSCCs: geminal, vicinal, 1,3-, and long-range constants.