ライフサイエンスコーパス: gem

1 gem-1 encodes a multipass transmembrane protein that is

2 gem-4 encodes a member of the copine family of Ca(2+)-de

3 gem-Dialkyl activation is necessary for these reactions

4 gem-Difluorinated styrenes, for which atom transfer reac

5 gem-Difluoroalkenes containing a number of functional gr

6 gem-Difluoroalkenes represent valuable synthetic handles

7 gem-Dimethyl substituents at the linker improved the pot

8 gem-Dimethyl substitution lowers the strain energy of cy

9 The 1'-(S)-methyl, 1'-gem-dimethyl, and 1'-cyclobutyl analogues exhibit remark

10 are 4 states in the relevant equilibrium: 1) gem-diol, 2) aldehyde, 3) hemiaminal, and 4) Schiff base

11 (R-allyl)LCl complexes [R = H, 1-Me, 1-Ph, 1-gem-Me(2), 2-Me; L = Q-Phos, P(t-Bu)(3), P(t-Bu)(2)(p-NM

12 19-oxo androgen and dehydration of the 19,19-gem-diol were shown to be catalytically competent.

13 nolized substrates in the presence of the 19-gem-diol decayed directly to the experimentally observed

14 [likely to bind as the hydrate, C(2)(OH)(2) gem-diol] as the most active substrates (for each, k(cat

15 a being either Gly (R(2) = H) or Aib (R(2) = gem-Me) and R(1) and R(3) either alkyl or amino acid sub

16 n of 1,1-difluoroallene, provides chiral 2,2-gem-difluorinated homoallylic alcohols in good yields an

17 Four of the ligands possess a C(4)-gem-dimethyl group and four a C(4)-gem-diphenyl group ad

18 ss a C(4)-gem-dimethyl group and four a C(4)-gem-diphenyl group adjacent to the C(5)-isopropyl substi

19 plexes of ligands 11a-h, along with non-C(4)-gem-disubstituted analogues 1a-g, were effective in the

20 Of these, analogues 50 (4,4-gem-difluoro) and 62 (4,4,4',4'-tetrafluoro) were highly

21 xide; insertion of phenylacetylene affords a gem-dicopper vinyl complex.

22 O)(OEt)(2))-7-(Me(2)S)B(12)H(10) (14g) and a gem-bisphosphonate 1-(MeS(CH(2))(3)CH[P(O)(OEt)(2)](2))-

23 ntains a trans-dialkyl group in ring D and a gem-dimethyl group in ring B.

24 Knoevenagel condensation of the latter and a gem-dimethyl, beta-ketoester-substituted BC dihydrodipyr

25 -bearing peridotite, its clinopyroxene and a gem-quality diamond.

26 c cage compounds, utilizing PhSCF2SiMe3 as a gem-difluoromethylene building block, is described.

27 density suggests one active site contains a gem-diamine intermediate with d-ornithine; the second ha

28 approximately 350 nm is assigned as either a gem-diamine complex or a thiol adduct formed by nucleoph

29 se results provide additional evidence for a gem-diol intermediate in the catalytic mechanism of kynu

30 -ACP appeared to be the sole route to form a gem-dimethylated product, while the yersiniabactin PKS c

31 The peptide forms a gem-diol tetrahedral reaction intermediate (TI) in the c

32 version is observed with substrates having a gem-carbonyl group.

33 DFOA binds in a gem-diol form analogous to the oxalacetate intermediate/

34 nd to provide synthetic methods to install a gem-dimethyl group.

35 The transformation involves a gem-diamine intermediate that undergoes the indolizidine

36 es both the enantiotopic leaving groups of a gem-diacetate and enantiotopic faces of the enolate of a

37 The observation of a gem-diamine intermediate provides insight into the confo

38 ed the pyrrolidine ring in the presence of a gem-difluoro moiety to avoid using potentially hazardous

39 With the strategic implementation of a gem-dimethyl group to promote both stability and cycliza

40 Introduction of a gem-dimethyl on the 6-position of the morpholin-2-one co

41 a complementary route employs reaction of a gem-dimethyl-substituted dihydrodipyrrin-carboxaldehyde

42 e mechanism that involves the formation of a gem-diol intermediate from the Zn bound uracil and a wat

43 The direct observation of a gem-diol intermediate provides further evidence that sup

44 e reaction mechanism involves formation of a gem-diol intermediate, whose decomposition into the prod

45 of water for hydrolysis, and formation of a gem-diol intermediate.

46 The mechanophore, based on a gem-dichlorocyclopropanated indene, is synthesized and u

47 drolysis occurring via an acyl-enzyme than a gem-diol intermediate.

48 amily of enzymes is thought to proceed via a gem-diol reaction intermediate, which has not been obser

49 within the active site of the enzyme when a gem-diol transition state analogue inhibitor is bound at

50 midine nucleosides have been modified with a gem diether moiety to yield the following new nucleoside

51 route to a model bacteriochlorophyll with a gem-dimethyl group in each pyrroline ring has been probe

52 e in which the O-O bond is broken to yield a gem diol species is structurally characterized.

53 In addition, gem-dimethyl substitution on the exocyclic double bond o

54 ted adducts 9 or alcohols 10 and 11 afforded gem-difluoromethylenated linear triquinanes 16 as an app

55 A variety of novel, bench-stable alkenyl gem-diboronate esters are synthesized.

56 and chirality transfer to afford alkylidene(gem-difluorocyclopropanes) incorporating a quaternary st

57 as a route toward functionalized alkylidene(gem-difluorocyclopropanes).

58 I) catalyst yielded a new class of (E)-allyl-gem-dipyrazole scorpionate ligands: 1-aryl-2-N-pyrazolyl

59 Allylic gem-dichlorides undergo regio- and enanantioselective (e

60 by a novel asymmetric alkylation of allylic gem-dicarboxylates.

61 ta-keto intermediate to yield an alpha,alpha-gem-dimethyl product, a new programing feature among HRP

62 gy for the monoprotodeboration of beta-amino gem-bis(boronate) precursors.

63 tho-chlorophenyl imine afforded a beta-amino gem-diiodide under the optimized reaction conditions due

64 The dehydrogenations of alcohol (Step 1) and gem-diol (Step 3) prefer the double hydrogen transfer me

65 -yl)carbamate (1) and its monomethyl (2) and gem-dimethyl analogues (3), were tested for activation b

66 studied by the reaction of trans-, cis-, and gem-ethylene-d2 upon activation of Cr(PNP(O4))(o,o'-biph

67 tinuous flow deuteriodifluoromethylation and gem-difluoroalkenylation of aldehydes.

68 ated by the presence of gem-dialkylsilyl and gem-dialkylstannyl groups in the precursors.

69 thesis of gem-diiodides, gem-dibromides, and gem-dichlorides.

70 ted with the ring opening of gem-dibromo and gem-dichlorocyclopropanes affixed along the backbone of

71 nzocyclobutene, gem-difluorocyclopropane and gem-dichlorocyclopropane require approximately 130 pN le

72 docyclization of gem-difluorohomoallenyl and gem-difluorohomopropargyl alcohols with I2 and ICl, resp

73 ds synthetically important fluoroalkenes and gem-difluoromethlylene compounds regioselectively.

74 rivatives as precursors to vinyl halides and gem-dihalides are described in detail.

75 on both coupling partners: heteroarenes and gem-dibromoalkenes.

76 nal aldimine and quinonoid intermediates and gem-diamine and external aldimine intermediates, respect

77 Fluoro, chloro, bromo, iodo, and gem-dihaloalkenes are viable substrates for the transfor

78 Reinstallation of the trans-olefin and gem-dimethyl group present in bryostatin 1 in Merle 48 r

79 ivity for hydroboration of cis-, trans-, and gem-disubstituted alkenes in excellent agreement with ex

80 ically, SMN localization to Cajal bodies and gems was not observed in cells derived from Zpr1-/- embr

81 uclear structures termed Cajal body (CB) and gems.

82 These results suggest that CBs and gems are kinetically independent structures.

83 e kinetics of multiple components of CBs and gems in living cells using photobleaching microscopy.

84 CBs and gems often colocalize, and communication between these s

85 (combining herbs with metals, minerals, and gems).

86 orm secondary homopropargyl alcohols bearing gem-dimethyl groups.

87 ly to ulosonic acid derivatives, all bearing gem-dialkyl, gem-cycloalkyl, and spirocyclic quaternary

88 substituted 1-alkenyl-5-pentyn-1-ols bearing gem-dialkyl substituents at either the C2, C3, or C4 pos

89 ring-opening reactions of benzocyclobutene, gem-difluorocyclopropane and gem-dichlorocyclopropane re

90 , indole-, and benzothiophene-based benzylic gem-diboronates, building blocks for biologically releva

91 , indole-, and benzothiophene-based benzylic gem-diboronates, via radical carbo-cyclization/gem-dibor

92 nd secondary alcohols to a range of branched gem-bis(alkyl) ketones.

93 ivation of type IA p110alpha PI3K and Akt by gem and abrogation of gem-induced upregulation of IL-1Ra

94 1beta-hydrogen atom abstraction followed by gem-diol deprotonation.

95 diate to produce P450 compound I and the C19 gem-diol likely proceeds with a low energetic barrier.

96 the stereoselective installation of the C2' gem-Br,F substitution and subsequent Vorbruggen glycosyl

97 vidently migrates from the sulfur atom to C3-gem-diol obtained by hydration of the keto group and the

98 bond (C-C and C-H) cleavages convert the C5 gem-dimethyl group to the C15 lactone of PXN.

99 the number of intranuclear particles called gems.

100 Twin structures, called gems, contain high concentrations of the survival motor

101 The structure reveals a catalytic gem diol nucleophile derived from modification of a cyst

102 ning of a cis-dialkyl substituted syn-chloro-gem-chlorofluorocyclopropane, in violation of the Woodwa

103 rs and in silico docking studies, the chloro-gem-dimethyl-anthracenone substructure seen in the fasam

104 The mechanochemical activation of cis-gem-difluorocyclopropane (cis-gDFC) mechanophore in tolu

105 Brittle crystals, such as coloured gems, have long been known to cleave with atomically smo

106 T domain is suggested to facilitate complete gem-dimethylation by the MT.

107 tion of the methodology to the corresponding gem-dialkoxy system was also explored to facilitate acce

108 uxing conditions to afford the corresponding gem-difluoromethylenated 1-azabicyclic compounds 10-13 i

109 ly consumed by KOH to give the corresponding gem-diolate and provides the overall driving force for t

110 m-diboronates, via radical carbo-cyclization/gem-diborylation of alkynes with a high functional group

111 resulting adducts 3 to provide the cyclized gem-difluoromethylenated diquinanes 4 as a mixture of st

112 Silver(I)-imidazole cyclophane gem-diol complex, 3 [Ag2C36 N10(O)4](2+)2(x)-, where x =

113 xicity of the ligand (imidazolium cyclophane gem-diol dichloride) was assessed by intravenous adminis

114 rapidly and chemoselectively to the desired gem-difunctionalized products in good to excellent yield

115 c acid derivatives, all bearing gem-dialkyl, gem-cycloalkyl, and spirocyclic quaternary centers.

116 ides, and in the synthesis of gem-diiodides, gem-dibromides, and gem-dichlorides.

117 r gem diether nucleosides, only the dimethyl gem diether congener showed significant antiviral activi

118 The only recently discovered gem-hydrogenation of internal alkynes is a fundamentally

119 e, extracts prepared from cells that display gems are less efficient in methylating coilin and Sm con

120 ilin is hypomethylated in cells that display gems, but not in those that primarily contain CBs.

121 clude the following: (1) a typically elusive gem-diamine intermediate is trapped in the enzyme comple

122 e with a difluorocarbene source, we embedded gem-difluorocyclopropanes (gDFCs) along the polymer back

123 Miyaura cross-coupling of optically enriched gem-diboronyl compounds with various aryl bromides.

124 Here we report that large, exceptional gem diamonds like the Cullinan, Constellation, and Koh-i

125 l rotaxanes have been synthesized to explore gem-dibromoethene moieties as "masked" polyynes.

126 Of the four gem diether nucleosides, only the dimethyl gem diether c

127 stituted 3,3-difluoro-4,5-dihydrofurans from gem-difluorohomopropargyl alcohols occurred in excellent

128 formation with different substituents, from gem-diol formation for electron-donating substituents to

129 blocks for the preparation of functionalized gem-difluorocyclopropanes.

130 Furthermore, gem was able to protect neurons from IL-1beta insult.

131 ne-bridged model compounds (16) and (18) (g, gem-diaminoalkyl; m, malonyl; and r, direction-reversed

132 derlines a novel application of gemfibrozil (gem), a Food and Drug Administration-approved lipid-lowe

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

134 ion of pyrroles and terminal alkynes to give gem-selective alpha-vinylpyrroles.

135 is is also the first report of selective C-H gem-difluorination.

136 Substrates having gem-hydrogen, -alkyl, or -alkenyl groups give products w

137 e system 1a/1a' without a change in the high gem regioselectivity.

138 that methylation can precede condensation in gem-dimethyl group producing PKS modules.

139 The Thorpe-Ingold effect in gem-dimethyl substituted enediynes enhances the efficien

140 We report here that mutations in gem-4 (gon-2 extragenic modifier) are capable of suppres

141 eases binding of coilin to SMN, resulting in gem formation.

142 hloride or iodotoluene difluoride results in gem-dichlorination or gem-difluorination products, respe

143 colocalizes with SMN in the cytoplasm and in gems.

144 he nucleus, where it colocalizes with SMN in gems.

145 a diverse array of cyclopentanes, including gem-disubstituted cyclopentanes having substitution on t

146 he flexible flaps of the PR by incorporating gem-difluorines and alkoxy, respectively, at the C4 posi

147 t novel bis(oxazoline) ligands incorporating gem-disubstitution on one of the oxazoline rings were pr

148 SMN protein levels and intranuclear gems also were significantly increased in these hydroxyu

149 three-component heterocyclization involving gem-bromofluorocyclopropanes, nitrosyl tetrafluoroborate

150 KMN-80 and its gem-difluoro analog KMN-159 possess high selectivity rel

151 2BF4(-)) exists in equilibrium with both its gem-diol and several aggregates (from dimers to at least

152 y both for substrates containing and lacking gem-dimethyl substitution.

153 l assemblages and reduced volatiles in large gem diamonds indicate formation under metal-saturated co

154 These little gems have a wide range of potential applications in trib

155 l)-4,5-dihydroimidazol-2-ylidene; R = H, Me, gem-Me2, Ph] have been synthesized and fully characteriz

156 ce of the PI3K-Akt-CREB pathway in mediating gem-induced upregulation of IL-1Ra in neurons and sugges

157 e word "crystal" invokes images of minerals, gems, and rocks, all of which are inevitably solid, hard

158 undergoing AlkDF include monofluoroalkanes, gem-difluorocyclopentane, and compounds containing a CF(

159 Cyclic polymers containing multiple gem-dichlorocyclopropane (gDCC) mechanophores along thei

160 The binding mode of the neutral gem-diol may mimic the binding of the neutral tetrahedra

161 The synthesis of a range of novel gem-disubstituted and electronically varied thiophene-ox

162 The synthesis of a range of novel gem-disubstituted ferrocene-oxazoline ligands and their

163 lso increased SMN protein levels and nuclear gem/Cajal body numbers in patient-derived cells.

164 merizes and interacts with Gemin2 in nuclear gems and axonal granules.

165 stribute to the cytoplasm and to the nuclear gems.

166 n most cell types, CBs coincide with nuclear gems, which contain the survival of motor neurons (SMN)

167 rotein, preventing the formation of nuclear 'gems' by disrupting the recruitment of the protein to Ca

168 function and increase the number of nuclear 'gems', small nuclear organelles in which survival motor

169 0alpha PI3K and Akt by gem and abrogation of gem-induced upregulation of IL-1Ra by inhibitors of PI3K

170 Efficient routes toward activation of gem-chlorofluorocyclopropane-derived (2-fluoroallyl)boro

171 rm the gem-diol (Step 2); dehydrogenation of gem-diol to carboxylic acid (Step 3); and deprotonation

172 egioselective unsymmetrical dioxygenation of gem-difluoroalkenes using phenols and molecular oxygen,

173 gesting that gon-4 either acts downstream of gem-4 and gon-2 or acts in a parallel regulatory pathway

174 al IL-1Ra abrogated the protective effect of gem against IL-1beta, suggesting that this drug increase

175 ystem has been extended to the generation of gem-difluorinated motifs which are commonly found in med

176 Enantioselective transfer hydrogenation of gem-dibenzoate 1e in the presence of aromatic, alpha,bet

177 Inactivation of gem-1 enhances the gonadogenesis defects of gon-2 hypomo

178 en-1-yl acetates through the intermediacy of gem-diacetates.

179 The iodocyclization of gem-difluorohomoallenyl and gem-difluorohomopropargyl al

180 The yields of both iodocyclization of gem-difluorohomopropargyl alcohol and subsequent Suzuki

181 In order to characterize the mechanism of gem-dimethyl group formation, with a goal toward enginee

182 Mutation of gem-4 does not suppress the gonadal defects produced by

183 e forces associated with the ring opening of gem-dibromo and gem-dichlorocyclopropanes affixed along

184 nonscissile mechanochemical ring opening of gem-dichlorocyclopropane mechanophores and (ii) the mole

185 eration of the electrocyclic ring opening of gem-dichlorocyclopropanes (gDCC) is sensitive to the ste

186 -dihalides is facilitated by the presence of gem-dialkylsilyl and gem-dialkylstannyl groups in the pr

187 ) radical addition furnishes a wide range of gem-difluoroalkenes through beta-fluoride elimination of

188 an asymmetric allylic alkylation reaction of gem-diacetate 9 with azlactone 10.

189 The radical-type ring-opening reaction of gem-difluorocyclopropanes and subsequent regioselective

190 most transition-metal-catalyzed reactions of gem-difluoroalkenes that typically involve defluorinatio

191 king advantage of the distinct reactivity of gem-difluoroalkenes, we present a cobalt-catalyzed regio

192 no- and di-hydrodehalogenative reductions of gem-dibromocyclopropanes are described, providing an eas

193 Rotation of gem-dimethyls in commonly used nitroxides causes spin ec

194 mpounds were prepared by the substitution of gem-dichlorovinylene with 1,2-benzenedithiol.

195 A method for the synthesis of gem-difluorinated nitroso compounds is described.

196 An asymmetric synthesis of gem-difluoromethylenated dihydroxypyrrolizidines and ind

197 tively, a convenient asymmetric synthesis of gem-difluoromethylenated linear triquinanes 16A can be a

198 An asymmetric synthesis of gem-difluoromethylenated linear triquinanes is described

199 The synthesis of gem-difluoromethylenated polycyclic cage compounds, util

200 employed as precursors for the synthesis of gem-difluoromethylenated tetracyclic cage lactols or tet

201 s of vinyl bromides, and in the synthesis of gem-diiodides, gem-dibromides, and gem-dichlorides.

202 eloped for the rapid asymmetric synthesis of gem-dimethyl and spirocyclopropyl norbornyl carboxylic a

203 trate a facile approach for the synthesis of gem-disubstituted cyclooctanoids, a motif found in sever

204 The trimerization of gem-ethylene-d2 has an isotope effect of 1.3(1), consist

205 n structures that also contain components of gems and coiled (Cajal) bodies.

206 structures that contain the known markers of gems and coiled bodies, and inhibits RNA pol I and pol I

207 intramolecular coupling of two C-H bonds on gem-dialkyl groups has remained an elusive transformatio

208 eveal that collapse of the carbinolamine (or gem-diamine) to give the final product is the rate-deter

209 difluoride results in gem-dichlorination or gem-difluorination products, respectively.

210 Phi(gem) = 0.32 for WT and His64Gln, and Phi(gem) = 0.85 for Val68Phe).

211 e quantum yield in this mutated protein (Phi(gem) = 0.32 for WT and His64Gln, and Phi(gem) = 0.85 for

212 We previously reported two gemini pollen (gem) mutants that produced twin-celled pollen arising fr

213 d in a quantitative increase in SMN-positive gems and an overall increase in detectable SMN protein.

214 es that maintain immature neural precursors (gem, zic2) requires the Acidic blob (AB) region in the N

215 r each enzyme, corresponding to the proposed gem-diol reaction intermediate, over a time scale of 1-2

216 n, Krohn photo-oxidation, and regioselective gem-dichlorination.

217 ive intermediate derived from 1A(+) requires gem-1,1-dihydoxo stereochemistry to perform O-O bond for

218 The compound restored gems numbers in type I SMA patient fibroblasts to levels

219 ed complexes reacted with CO to form rhodium gem-dicarbonyls, which, in the presence of ethylene, gav

220 alable route to access functional-group-rich gem-difluoroalkenes.

221 This circular RNA gemmed from alternative splicing of Lrp6 (lipoprotein re

222 hree hydrolysis reactions may share the same gem-diol intermediate.

223 Alternatively, some gem-disubstituted cyclopropenes give dimerizations of th

224 y crystal structure shows that the squaraine gem-dimethyl groups force a relatively wide separation b

225 along the backbone of purely cis-substituted gem-difluorocyclopropanated polybutadiene using the exte

226 rding a wide range of heteroatom-substituted gem-difluoroalkenes, along with Doyle-Kirmse rearrangeme

227 w mechanoacid based on 2-methoxy-substituted gem-dichlorocyclopropane (MeO-gDCC).

228 Such gem-hydrogenation of stable carbogenic compunds is a fun

229 pregulation of IL-1Ra in neurons and suggest gem as a possible therapeutic treatment for propagating

230 ective synthesis of the desired C2-symmetric gem-difluoromethylenated angular triquinanes 6 in good y

231 A synthesis of symmetrical gem-difluoromethylenated angular triquinanes is describe

232 sion of a CRH-1/CREB transcriptional target (gem-4 Copine), which parallels the effects of human Shan

233 rious central functional groups and terminal gem-dimethyl or -methyl/aryl substituents was synthesize

234 and diols with a 13-atom chain and terminal gem-dimethyl substituents.

235 During this synthesis, it was found that gem-hydrogenation also provides opportunities for C-H fu

236 These studies reveal that gem-disubstitution of i-Pr-containing ferrocene oxazolin

237 These investigations show that gem-disubstitution of i-Pr-PHOX-type ligands can lead to

238 The gem-dimethyl effect is the acceleration of cyclization b

239 The gem-dimethyl groups in polyketide-derived natural produc

240 The gem-dimethyl moiety is a structural feature frequently f

241 fering RNA attenuation of CREB abolished the gem-mediated increase in IL-1Ra.

242 In addition, the gem-dimethyl series of analogues seem to display improve

243 plex with Mg(2+) and a substrate analog: the gem-diol of 3,3-difluoro-oxaloacetate) was determined fo

244 ing the central ketone functionality and the gem dimethyl or methyl/aryl substituents.

245 ting the central ether functionality and the gem dimethyl or methyl/aryl substituents.

246 onal studies suggest that the trans- and the gem-pathway have similar barriers, but polar substituent

247 due to a syn pentane interaction between the gem-dimethyl groups on the 2,2,6,6-tetramethylpiperidiny

248 dicinal chemists have elegantly employed the gem-dimethyl group to obtain clinically useful drugs and

249 that inhibitors that too strongly favor the gem-diol configuration have decreased potency due to low

250 or potency, with inhibitors that favored the gem-diol conformation exhibiting greater potency.

251 The Thorpe-Ingold hypothesis for the gem-dimethyl effect in the cyclization reactions of 2-ch

252 ; coupling of aldehyde and water to form the gem-diol (Step 2); dehydrogenation of gem-diol to carbox

253 itor aldehyde moiety is hydrated to form the gem-diol: one hydroxyl group bridges the Mn(2+)(2) clust

254 the corresponding steps that start from the gem-diolate and formate.

255 g closing metathesis reaction to furnish the gem-difluoromethylene containing cyclopentene, cyclohept

256 If the gem dimethyl groups of (+)-alpha-pinene occupied similar

257 he latter structures clearly illustrates the gem-dimethyl effect.

258 pressed by gain-of-function mutations in the gem-1 (gon-2 extragenic modifier) locus.

259 to the pro-S methylene carbon of ACC in the gem-diamine complexes, implicating a direct role of this

260 novel compounds containing this moiety, the gem-dimethyl group producing polyketide synthase (PKS) m

261 to address the challenging synthesis of the gem-difluoro group present in an opioid receptor-like 1

262 ubsequent cascade radical cyclization of the gem-difluoroalkyl radical generated from silylated adduc

263 nd E-W routes lie in (1) the location of the gem-dimethyl group (with respect to the 1-acetal unit) a

264 found to be sensitive to the location of the gem-dimethyl group.

265 udies described herein entail the use of the gem-dimethyl moiety as a means of improving the pharmaco

266 One of the gem-diol hydroxide groups in the PRWT complex forms a ve

267 he following two steps: (1) formation of the gem-diol intermediate and (2) cleavage of the peptide bo

268 arrier of 22.4 kcal/mol for formation of the gem-diol intermediate is 3.3 kcal/mol higher than for th

269 the oxygen exchange is the formation of the gem-diol intermediate, which is also the rate determinin

270 anticipated rate accelerations based on the gem-dimethyl effect are nonexistent and that substituent

271 oton on the ring nitrogen rather than on the gem-dinitro carbon results in extensive hydrogen-bonding

272 tion under thermal conditions to provide the gem-difluoroalkenylated product.

273 These results suggested that removing the gem-dimethyl group and flattening the ring would enhance

274 We found that the gem-diethyl nitroxide-labeled Bax variants were reasonab

275 Solution-state studies show that the gem-dimethyl groups in 3,3-dimethylindoline squaraine dy

276 Thus, the gem-dimethyl acceleration of oxirane formation for 1-3 i

277 by a vic-difluoro unit when compared to the gem-difluoro counterparts.

278 at least some thermodynamic component to the gem-dimethyl effect.

279 y positioning an oxygen atom adjacent to the gem-dimethyl-substituted carbon in 5 was properly realiz

280 503, Tyr532, and Phe533 interacting with the gem-dimethyl group.

281 t is excluded from the coiled bodies and the gems.

282 The "gem-bound" B(3)H(8) group itself has an atypical structu

283 lved as the days of stumbling on therapeutic gems, such as aspirin, have long passed and have been re

284 The utility of these gem-diboronates has been demonstrated by a 10 g scale co

285 In this gem, we discuss the unique position BAF occupies at the

286 ntaining inhibitors and relate these data to gem-diol formation.

287 12 and trans-13 were readily transformed to gem-difluoromethylenated dihydroxypyrrolizidines 20 and

288 M), all aggregates break up and the keto-to-gem-diol equilibrium is shifted quantitatively toward th

289 Using gem-difluoromethylene alkynes as effectors, unprecedente

290 ording the corresponding and highly valuable gem-difluoro esters.

291 A vinylogous gem effect was observed for the gamma,delta-dimethylated

292 The vinylogous gem effect favors the formation of 1,3-dienes from the s

293 The vinylogous gem effect is rationalized by DFT calculations showing t

294 When gem-dichlorocyclopropane (gDCC) copolymers derived from

295 est and lowest on the cultivars Vaila-winter gem and Dazzle respectively, and much higher in endophyt

296 With gem-disubstituted cyclopropenes, a novel cycloisomerizat

297 A cross-coupling of acyl chlorides with gem-difluorinated organozinc reagents affording difluori

298 moieties enhances catalytic efficency, with gem-dialkyl effect accelerations of 4.5 and 9.1, respect

299 lobutane is a four-membered carbon ring with gem-dimethyl substituents.

300 onfirm the importance of n(F) --> sigma*(C-Y)gem, where Y = H, C, O, S, hyperconjugative interactions