英语翻译
Thereadilyavailablestartingmaterial1waspreparedin
ourpreviouscontributions.10Sixhexylgroupswereattached
totheC-5,C-10,andC-15positionsofthetruxenemoiety
toincreasesolubilityaswellastoreleaseintermolecularπ-π
stacking.AsshowninScheme1,withacontrolledamount
ofiodineandperiodicacidhydrate,selectiveelectrophilic
iodinationatonebranchofthetruxenesegmentafforded
themonosubstitutedtruxeneiodide2ingoodyield(83%).11
Undernitrogenatmosphere,additionofn-butyllithiumat-78
CfollowedbyadditionofB(OCH3)3,hydrolysisby50%H2SO4aqueoussolution,andesterificationby1,3-propyldiol
generatedester3inmoderateyield(43%).Thestandard
Suzukicouplingreaction12between3and2,7-dibromo-9,9-
spirobifluorene(4)13withPd(PPh3)4ascatalystintoluene
providedthetargetmoleculeTM1efficiently(86%).
TM2waspreparedbyrepetitivepalladium-catalyzed
Sonogashiracouplingreactionfrom2(Scheme2).Acetylenic
alcohol5wasreadilyobtainedviatheSonogashiracoupling
[Pd(PPh3)4,CuI,Et3N]ofiodide2and2-methylbut-3-yn-
2-ol.14Itshouldbenotedthattheutilizationof2-methylbut-
3-yn-2-olinsteadoftrimethylsilylacetylene(TMSA)is
necessarytoobtainpureintermediate,duetotheincreased
polaritydifferencebetweenthestartingmaterialandthe
product.Theone-potSonogashiracouplingbetweenthe
acetylenicalcohol5andaryliodide2tookplaceinatwo-
phaseheterogeneoussysteminthepresenceofaphase-
transferreagentandanaqueousbase.15Underthesecondi-
tions,acetylenealcohol5transformedintothearylethyne
intermediate,whichcoupledwitharyliodide2immediately.
50大洋