Hydrazone-palladium catalyzed annulation of 1-allyl-2-bromobenzene derivatives with internal alkynes

Article abstract of DOI:10.1039/c5ob01959a

Annulation of 1-allyl-2-bromobenzene derivatives with internal alkynes using a hydrazone-palladium catalyst system proceeded smoothly and gave the corresponding polysubstituted naphthalene derivatives in good to high yields.

Full text of DOI:10.1039/c5ob01959a

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DOI: 10.1039/C5OB01959A
Journal(Name(
(
ARTICLE(
Hydrazone9palladium(catalyzed(annulation(of(
(
19allyl929bromobenzene(derivatives(with(internal(alkynes(
Received(00th(January(20xx,(
Accepted(00th(January(20xx(
Kohei(Watanabe,a(Takashi(Mino,a,b*(Chikako(Hatta,a(Shisei(Itoa(and(Masami(Sakamotoa,b(
DOI:(10.1039/x0xx00000x(
Annulation( of( 1BallylB2Bbromobenzene( derivatives( with( internal( alkynes( using( a( hydrazoneBpalladium( catalyst( system(
proceeded(smoothly(and(gave(the(corresponding(polysubstituted(naphthalene(derivatives(in(good(to(high(yields.(
www.rsc.org/obc
(
R1
R1
R2
Ph
N
N
N
N
R2
N
N
N
Introduction(
Me
Polysubstituted( naphthalene( derivatives( have( become(
interestingly(important(because(of(their(potential(utility(as(πB
conjugated( functional( materials,( such( as( organic(
semiconductors( and( luminescent( materials.1( Furthermore,(
they( are( also( basic( skeletons( of( many( biologically( active(
compounds( and( pharmaceuticals( such( as( an( inhibitor( of(
glycogen(synthase(kinaseB3((GSKB3).2(Therefore,(the(synthetic(
methodologies( for( such( structures( have( attracted( significant(
attention( and( been( developed.3( Among( modern( potential(
strategies(to(prepare(polysubstituted(naphthalene(derivatives(
are(the(metal(catalyzed(coupling(of(aromatic(compound(with(
two(internal(alkynes.4(In(2014,(Pham(and(coBworkers(reported(
RhBcatalyzed( annulation( of( directing( groupBfree( monocyclic(
arenes( with( two( internal( alkynes( via! CBH( activation( for(
synthesis( of( polysubstituted( naphthalenes.4p( However,( the(
products( of( these( methods( are( very( restricted( in( terms( of(
substituents( of( product( because( they( are( derived( from( two(
internal(alkynes.(On(the(other(hand,(there(are(some(examples(
of( the( intramolecular( annulation( without( internal( alkyne( for(
polysubstituted( naphthalene( derivatives,( but( these( protocol(
required( installing( substituent( in( design( of( starting( materials(
for( selective( synthesis.5( In( 2002,( Larock( and( coBworkers(
reported(that(polysubstituted(naphthalene(can(be(prepared(by(
annulation(of(o+alkenylaryl(halides(with(internal(alkynes(using(
a(triphenylphosphineBpalladium(catalyst(system.6(This(protocol(
via! intramolecular( Heck( reaction( is( very( effective( for( a(
selective( approach( to( trisubstituted( naphthalenes( with( the(
object(of(installing(various(substituents.(However,(this(protocol(
is( strongly( limited( in( terms( of( substrates.( For( instance,( the(
2
1
1a: R1 = Ph, R2 = Me
1b: R1 = 2-Pyridyl, R2 = Me
1c: R1, R2 = -(CH2)4-
1d: R1, R2 = -(CH2)5-
1e: R1, R2 = -(CH2)6-
(
Figure(1(Hydrazones(1(and(2.(
main( starting( materials( of( annulation( are( aryl( iodides,( which(
are(reactive(but(expensive.(Furthermore,(all(starting(materials(
aside(from(one(have(electronBdeficient(olefin.(When(1BallylB2B
iodebenzene,( whose( olefin( has( no( substituent,( reacted( with(
diphenylacetylene,( the( corresponding( naphthalene( product(
was(obtained(in(only(32%(yield.6b(On(the(other(hand,(Chen(and(
coBworkers(reported(similar(reaction(which(was(achieved(by(CB
H(bond(activation.7(However,(this(protocol(was(also(tolerated(
only( electronBdeficient( olefin( bearing( a( phenyl( group( and(
required( Cu(OAc)2( as( a( coBcatalyst( in( the( presence( of( excess(
amount(of(TFA.
ꢀ We( recently( demonstrated( phosphine( free( hydrazone(
compounds( (Figure( 1)( as( an( effective( ligands( for( palladiumB
catalyzed( CBC( bond( formations( such( as( the( MizorokiBHeck,8(
SuzukiBMiyaura,9( Sonogashira10( and( Hiyama10( crossBcoupling(
reactions(of(aryl(halides.(Herein,(we(report(how(limitation(of(
substrates(on(palladiumBcatalyzed(annulation(of(aryl(bromides(
with( internal( alkynes( for( synthesis( of( polysubstituted(
naphthalene(derivatives(would(be(solved(by(using(hydrazone(
as(a(ligand.(
Results(and(discussion(
Initially,( we( sought( the( optimal( reaction( conditions( for( a(
palladiumBcatalyzed(synthesis(of(polysubstituted(naphthalenes(
using( hydrazone( ligands.( The( reaction( using( 1BallylB2B
(This(journal(is(©(The(Royal(Society(of(Chemistry(20xx!
J.!Name.,(2013,(00,(1B3(|(1((
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bromobenzene( and( diphenylacetylene( as( model( substrates( Using(hydrazone(ligands(1cBe(bearing(5B7(member(rings(gave(
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DOI: 10.1039/C5OB01959A
was(performed(under(an(argon(atmosphere(at(90(°C(for(24(h( the( corresponding( product( in( 42%,( 58%( and( 29%( yields,(
(Table(1).(Using(Pd(OAc)2(and(bishydrazone(1a(as(a(ligand,(we( respectively( (Table( 1,( entries( 10B12).( In( the( case( of( using(
observed(that(the(reaction(in(the(presence(of(Cs2CO3(in(DMF(as( pyridineBtype( monohydrazone( ligand( 2,( the( desired( product(
a(solvent(gave(corresponding(product(5aa(in(41%(yield((Table(1,( was( obtained( in( 45%( yield( (Table( 1,( entry( 13).( On( the( other(
entry( 1).( Several( palladium( sources( were( tested( (Table( 1,( hand,( the( reaction( proceeded( inefficiently( using(
entries( 2B8).( When( we( used( Pd(TFA)2,( product( 5aa( was( triphenylphosphine(as(a(ligand(and(gave(the(desired(product(in(
obtained(in(67%(yield((Table(1,(entry(6).(On(the(other(hand,( a(low(yield((Table(1,(entry(14).(As(a(result,(we(found(phenylB
palladium(0)( sources,( such( as( Pd2(dba)3( and( Pd(PPh3)4( were( methylBtype(bishydrazone(ligand(1a(was(the(most(suitable(for(
not(effective(for(this(reaction((Table(1,(entries(7(and(8).(Next,( this(annulation((Table(1,(entry(6).(Next,(the(effects(of(various(
we(tested(hydrazone(ligands(1aBe(and(2((Table(1,(entries(6(and( bases(were(investigated((Table(1,(entries(6(and(15B19).(Using(
9B14).( While( phenylBmethylBtype( bishydrazone( ligand( 1a( Cs2CO3(led(to(the(highest(yield(in(this(reaction((Table(1,(entry(
afforded( the( corresponding( product( in( high( yield( (Table( 1,( 6).( Various( solvents( were( also( tested( (Table( 1,( entries( 6( and(
entry( 6),( 2BpyridylBmethylBtype( bishydrazone( ligand( 1b( 20B24).( DMF( was( the( most( suitable( solvent( for( this( reaction(
afforded(slightly(lower(yield(of(product((Table(1,(entry(9).((
(Table(1,(entry(6).(
((
ꢀ With( the( optimized( reaction( conditions( in( hand( (Table( 1,(
Entry(6),(we(reacted(1BallylB2Bbromobenzene(derivatives(3(with(
Table( 1(Optimization(of(palladiumBcatalyzed(annulation(of(1B internal( alkynes( 4( at( 80B110( °C( to( investigate( the( scope( and(
allylB2Bbromobenzene( (3a)( with( diphenylacetylene( (4a)( using( limitation(of(this(annulation((Table(2).(The(reactions(of(1BallylB
hydrazone(ligand.a(
2Bbromobenzenes( with( an( electronBdonating( or( withdrawing(
group( at( the( 5Bposition( of( the( aromatic( ring( and(
diphenylacetylene( 4a( proceeded( and( gave( corresponding(
products(in(good(to(high(yields(respectively((Table(2,(entries(2B
5).( Furthermore,( 4BmethylBsubstituted( aryl( bromide( 3f( was(
also(tolerated((Table(2,(entry(6).(Aryl(bromide(3g(bearing(two(
methoxy(groups(on(the(aromatic(ring(reacted(with(4a(at(110(°C(
to(afford(the(desired(product(5ga(in(good(yield((Table(2,(entry(
7).( Moreover,( we( also( succeeded( in( synthesizing(
polysubstituted( phenanthrene( derivative( 5ha( in( 66%( yield(
(Table(2,(entry(8).(The(reaction(of(bromide(3i,(whose(olefin(has(
a( phenyl( group,( gave( the( corresponding( product( 5ia( in( high(
yield((Table(2,(entry(9).(On(the(other(hand,(the(annulation(of(3j,(
which(has(a(prenyl(group,(did(not(afford(the(desired(product(
(Table(2,(entry(10).(Presumably,(this(result(indicated(that(bulky(
olefin(bearing(no(electronBwithdrawing(group(did(not(undergo(
an( intramolecular( Heck( reaction( because( of( steric( and(
electronic( effects.( Next,( we( tested( the( reaction( of( 1BallylB2B
bromobenzene((3a)(with(various(symmetrical(internal(alkynes(
4.( When( we( employed( diaryl( acetylenes( bearing( electronB
donating( or( withdrawing( substituents( on( the( aryl( ring,( the(
corresponding( products( were( also( obtained( in( good( yields(
(Table( 2,( entries( 11B14).( However,( the( product( was( not(
observed(in(the(case(of(using(diBp+cyanophenyl(acetylene((4f).(
This( result( indicated( that( internal( alkyne( bearing( strong(
electronBwithdrawing( groups( does( not( have( enough(
coodination(force(to(palladium(complex(because(of(the(lack(of(
electron( density( on( the( triple( bond( of( the( internal( alkyne(
(Table(2,(entry(15).(Aliphatic(internal(alkyne(such(as(4Boctyne(
(4g)( was( tolerated( and( afforded( the( desired( product( 5ag( in(
65%( yield.( Unfortunately,( the( desired( product( was( not(
obtained( from( the( reaction( of( 1BallylB2Bbromobenzene( (3a)(
with(diethyl(acetylenedicarboxylate((4h)(because(of(the(same(
reason(in(the(cace(of(4f((Table(2,(entry(17).(On(the(other(hand,(
the( use( of( an( acetylBprotected( 2BbutyneB1,4Bdiol( resulted( in(
obtaining( a( naphthalene( product( 5ai( in( 56%( yield( (Table( 2,(
entry(18).(In(the(case(of(using(unsymmetric(internal(alkyne(4j,(
Ph
Catalyst (Pd = 10 mol%)
Ligand (10 mol%)
+
Ph
Base (2.0 equiv.)
Solvent (0.5 M)
Ar, 90 °C, 24 h
Br
Ph
Ph
5aa
3.0 equiv.
3a
4a
(
Yield(of((
Entry( Catalyst(
Ligand( Base(
Solvent(
5aa([%](
1(
2(
3(
4(
5!
6(
7(
8(
9(
Pd(OAc)2(
1a(
1a(
Cs2CO3( DMF(
Cs2CO3( DMF(
Cs2CO3( DMF(
Cs2CO3( DMF(
Cs2CO3! DMF!
Cs2CO3( DMF(
Cs2CO3( DMF(
Cs2CO3( DMF(
Cs2CO3( DMF(
Cs2CO3( DMF(
Cs2CO3( DMF(
Cs2CO3( DMF(
Cs2CO3( DMF(
Cs2CO3( DMF(
41(
57(
14(
55(
47!
67(
PdCl2(
3
[Pd(η Ballyl)]2( 1a(
Pd(acac)2(
PdCl2(MeCN)2! 1a!
Pd(TFA)2(
Pd2(dba)3(
Pd(PPh)4(
Pd(TFA)2(
1a(
1a(
1a(
9(
1b(
1c(
1d(
1e(
2(
PPh3
1a(
1a(
1a(
1a(
1a(
1a(
1a(
1a(
1a!
1a(
8(
24(
50(
42(
58(
29(
45(
17(
15(
10( Pd(TFA)2(
11( Pd(TFA)2(
12( Pd(TFA)2(
13( Pd(TFA)2(
14( Pd(TFA)2(
15( Pd(TFA)2(
16( Pd(TFA)2(
17( Pd(TFA)2(
18( Pd(TFA)2(
19( Pd(TFA)2(
20( Pd(TFA)2(
21( Pd(TFA)2(
22( Pd(TFA)2(
23( Pd(TFA)2!
24( Pd(TFA)2(
b(
K2CO3(
K3PO4(
DMF(
DMF(
25(
Ca(OH)2( DMF(
NaOAc( DMF(
Trace(
Trace(
Trace(
28(
42(
29(
Et3N(
DMF(
Cs2CO3( DMA(
Cs2CO3( NMP(
Cs2CO3( DMSO(
Cs2CO3! 1,4BDioxane! 41!
Cs2CO3( PhMe( 39(
a( Reaction( conditions:( 3a,( 4a( (3.0( equiv.),( catalyst( (Pd( =( 10(
mol%),(ligand((10(mol%),(base((2.0(equiv.),(solvent((0.5(M)(at(
90(°C(for(24(h(under(Ar.(b(20(mol%(of(PPh3(was(added.(
the(
reaction(
gave(
2(|(J.!Name.,(2012,(00,(1B3(
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Table(2(Scope(and(limitation(of(annulation(of(aryl(bromide(3(with(internal(alkynes(4(using(hydrazone(ligand.a(
View Article Online
DOI: 10.1039/C5OB01959A
R3
R2
R5
R3
R4
Pd(TFA)2 (10 mol%)
1a (10 mol%)
6
5
R1
R2
+
R1
Cs2CO3 (2.0 equiv.)
DMF (0.5 M)
4
Br
R5
3
R4
3.0 equiv.
Ar, 90 °C, 24 h
3
4
5
(
Entry(
R1(
R2(
R3(
R4(
R5(
Yield&of&5!(%)(
1(
H(
5BMeO(
5BMe(
5BCl(
5BF(
4BMe(
4,5BdiMeO(
B(CH=CH)2B!(3,4)( H(
H(
5BMeO(
H(
H(
H(
H(
H(
H(
H(
H(
H(
H(
H(
H(
H(
H(
H(
H(
H"(3a)(
H"(3b)(
H"(3c)(
H"(3d)(
H"(3e)(
H"(3f)(
H"(3g)(
H"(3h)(
H!(3i)(
Me#(3j)(
H"(3a)(
H"(3a)(
H"(3a)(
H"(3a)(
H"(3a)(
H"(3a)(
H"(3a)(
H"(3a)(
H"(3a)(
Ph(
Ph(
Ph(
Ph(
Ph(
Ph(
Ph(
Ph(
Ph#(4a)(
Ph#(4a)(
Ph#(4a)(
Ph#(4a)(
Ph#(4a)(
Ph#(4a)(
Ph#(4a)(
Ph#(4a)(
Ph#(4a)(
Ph#(4a)(
67#(5aa)(
57#(5ba)(
60#(5ca)(
47#(5da)(
50#(5ea)(
58#(5fa)(
71#(5ga)(
66"(5ha)(
81#(5ia)(
N.D.e!(5ja)(
2(
3b!
4!
5c!
6d(
7d(
8(
9!
Ph(
Ph(
Ph(
10(
11b(
12!
13b(
14b!
15(
16b!
17(
18b!
19d(
Me(
H(
H(
H(
H(
H(
H(
H(
H(
H(
pBMeOC6H4(
pBMeC6H4(
pBClC6H4(
pBFC6H4(
pBNCC6H4(
nBPr(
COOEt(
CH2OAc(
Me(
pBMeOC6H4!(4b)( 60#(5ab)(
pBMeC6H4!(4c)(
pBClC6H4!(4d)(
pBFC6H4!(4e)(
pBNCC6H4!(4f)(
nBPr#(4g)(
COOEt%(4h)(
CH2OAc$(4i)(
Ph#(4j)(
50#(5ac)(
64#(5ad)(
65#(5ae)(
N.D.e!(5af)(
65#(5ag)(
N.D.e!(5ah)(
56#(5ai)(
62f!(5aj+5aj’)(
a(Reaction(conditions:(Aryl(bromide(3,(internal(alkyne(4((3.0(equiv.),(Pd(TFA)2((10(mol%),(1a((10(mol%),(Cs2CO3((2.0(equiv.),(DMF((0.5(M)(at(
90(°C(for(24(h(under(Ar.(b(This(reaction(was(carried(out(at(100(°C.(c(This(reaction(was(carried(out(at(80(°C.(d(This(reaction(was(carried(out(at(
110(°C.(e(Not(detected.(f(The(ratio(of(5aj/5aj’(was(9/1(by(1H(NMR(analysis.(
oxidative( addition( of( aryl( bromide( occurs( and( hydrazoneB(
palladium(0)(species(inserts(into(carbonBbromide(bond(of(1BallylB2B(
bromobenzene( to( generate( arylBpalladium(II)( complex( I.( Next,( a(
Base + HBr
Br
Pd(0)
Base
triple(bond(of(internal(alkynes(coordinates(to(palladium(complex(I(
and(inserts(into(a(carbonBpalladium(bond(of(complex(I(to(generate(
HPd(II)Br
R
intermediate( II.( Subsequently,( Intramolecular( Heck( reaction( of(
intermediate( II( forms( alkyl( palladium(II)( species( III.( alkylB
palladium(II)( species( III( undergoes( βBhydride( elimination( to(
generate( intermediate( IV( and( hydrideBpalladium(II)( species.(
Intermediate( IV( easily( transforms( to( the( aromatic( product( via(
aromatization.(On(the(other(hand,(after(the(reductive(elimination(
of( HBr( from( hydrideBpalladium(II)( species( by( base,( hydrazoneB
palladium(0)( species( is( regenerated( and( the( catalytic( cycle( is(
completed.( We( thought( these( palladium( complexes( were(
stabilized( by( hydrazone( ligand,( and( this( reaction( proceeded(
smoothly( in( spite( of( the( use( of( aryl( bromides( without( electronB
deficient(olefin.(
R
Pd(II)Br
I
R
R
Aromatization
Pd(II)Br
Pd(II)Br
R
R
H
R
IV
R
R
II
R
III
Scheme(1(Plausible(reaction(mechanism
(
1,3BdimethylB2Bphenylnaphthalene( (5aj)( and( 1,2BdimethylB3B
phenylnaphthalene((5aj’)((5aj/5aj’(=(9/1)((Table(2,(entry(19).(
ꢀ A(plausible(mechanism(of(annulation(of(1BallylB2Bbromobenzene(
derivatives(with(internal(alkynes(is(illustrated(in(Scheme(1.(At(first,ꢀ
(Conclusions(
This(journal(is(©(The(Royal(Society(of(Chemistry(20xx!
J.!Name.,(2013,(00,(1B3(|(3(
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(
In(summary,(we(found(that(palladiumBcatalyzed(annulation(of(
1BallylB2Bbromobenzene(derivatives(3(with(internal(alkynes(4(
using(hydrazone(1a(as(a(ligand(proceeded(smoothly(and(gave(
the(corresponding(polysubstituted(naphthalene(derivatives(5(
in(good(to(high(yields(even(though(low(reactive(aryl(bromides(
without( electronBdeficient( olefin( were( employed( as( starting(
materials.(
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ꢀ
69Fluoro939methyl91,29diphenylnaphthDalOeIn: e10( .1(053e9a/)C(5(OTBa0b1le9(592A,(
Entry(5)(
Compound(5ea(was(obtained(according(to(the(general(procedure(
at(80(°C(in(50%(yield((0.0386(g,(0.12(mmol);(White(solid;(m.p.(147B
149(°C;(1H(NMR((300(MHz,(CDCl3):(δ(7.70((s,(1H),(7.48B7.41((m,(2H),(
7.23B7.00((m,(11H),(2.24((s,(3H);(13C(NMR((75(MHz,(CDCl3):(δ(162.3,(
159.0,( 140.3,( 139.2,( 139.1,( 138.7,( 135.8,( 133.7( (d,( J( =( 9.3( Hz),(
130.9,( 130.1,( 129.5( (d,( J( =( 8.8( Hz),( 128.4,( 127.5( (d,( J( =( 5.0( Hz),(
126.7((d,(J(=(5.3(Hz),(126.3((d,(J(=(21.8(Hz),(115.3((d,(J(=(24.9(Hz),(
109.9( (d,( J( =( 20.2( Hz),( 21.9;( EIBMS( m/z( (rel( intensity):( 312( (M+,(
100);( HRMS( (APPI):( calcd( for( C23H17F( [M]+( 312.1309,( found(
312.1302.(
Experimetal(section((
Representative(procedure(for(hydrazone9Pd(catalyzed(annulation.(
(
A(mixture(of(aryl(bromide(3((0.25(mmol),(internal(alkyne(4((0.75(
mmol),(Pd(TFA)2((8.31(mg,(0.025(mmol),(hydrazone(ligand(1a((6.66(
mg,(0.025(mmol),(and(Cs2CO3((0.1630(g,(0.50(mmol)(in(DMF((0.5(
mL)( under( an( Ar( atmosphere( was( stirred( for( 24( h( at( 80B110( °C.(
After(the(reaction,(the(reaction(was(quenched(with(distilled(water.(
The(solution(was(extracted(with(ethyl(acetate,(washed(with(brine,(
dried( over( anhydrous( MgSO4,( and( concentrated( under( reduced(
pressure.( The( residue( was( purified( by( silica( gel( chromatography(
(hexane,( hexane/ethyl( acetate( (v/v( =( 100B10/1)( or(
hexane/chloroform((v/v(=(1/1))(to(afford(the(product(5.(
(
ꢀ 3,79Dimethyl91,29diphenylnaphthalene((5fa)((Table(2,(Entry(6)(
Compound(5fa(was(obtained(according(to(the(general(procedure(
at( 110( °C( in( 58%( yield( (0.0447( g,( 0.15( mmol);( White( solid;( m.p.(
134B135(°C;(1H(NMR((300(MHz,(CDCl3):(δ(7.74((d,(J(=(8.5(Hz,(1H),(
7.72((s,(1H),(7.30((dd,(J(=(8.3,(1.6(Hz,(1H),(7.22B7.07((m,(9H),(7.03B
7.00((m,(2H),(2.36((s,(3H),(2.23((s,(3H);(13C(NMR((75(MHz,(CDCl3):(δ(
140.7,(139.9,(139.5,(137.9,(134.8,(133.3,(131.3,(131.1,(131.0,(130.1,(
128.0,( 127.43,( 127.36,( 127.1,( 127.0,( 126.2,( 126.0,( 125.6,( 21.9,(
21.8;(EIBMS(m/z((rel(intensity):(308((M+,(100);(HRMS((APCI):(calcd(
for(C24H21([M(+(H]+(309.1638,(found(309.1628.(
(
ꢀ 39Methyl96,79dimethoxy91,29diphenylnaphthalene((5ga)((Table(
2,(Entry(7)(
ꢀ 39Methyl91,29diphenylnaphthalene((5aa)6b((Table(1,(Entry(6)(
Compound(5aa(was(obtained(according(to(the(general(procedure(
at(90(°C(in(67%(yield((0.0493(g,(0.17(mmol);(White(solid;(m.p.(149B
151(°C;(1H(NMR((300(MHz,(CDCl3):(δ(7.84((d,(J!=(7.9(Hz,(1H),(7.77((s,(
1H),(7.45((t,(J!=(7.7(Hz,(2H),(7.31((td,(J!=(6.6,(1.8(Hz,(1H),(7.23B7.08(
(m,(8H),(7.03((dt,(J!=(6.4,(3.6(Hz,(2H),(2.26((s,(3H);(13C(NMR((75(
MHz,( CDCl3):( δ( 140.6,( 139.8,( 139.4,( 139.1,( 138.6,( 134.4,( 132.9,(
131.3,(131.0,(130.1,(127.5,(127.4,(127.1,(126.8,(126.3,(126.1,(125.7,(
125.2,(21.9;(EIBMS(m/z((rel(intensity):(294((M+,(100).(
Compound(5ga(was(obtained(according(to(the(general(procedure(
at(110(°C(in(71%(yield((0.0624(g,(0.18(mmol);(Yellow(solid;(m.p.(
203B205(°C;(1H(NMR((300(MHz,(CDCl3):(δ(7.63((s,(1H),(7.23B7.08((m,(
9H),(7.04B7.01((m,(2H),(6.76((s,(1H),(4.02((s,(3H),(3.69((s,(3H),(2.22(
(s,( 3H);( 13C( NMR( (75( MHz,( CDCl3):( δ( 149.3,( 148.8,( 140.8,( 140.0,(
138.1,(137.4,(132.6,(130.8,(130.2,(128.7,(127.5,(127.4,(126.6,(126.3,(
126.0,( 125.9,( 105.61,( 105.56,( 55.9,( 55.5,( 21.7;( EIBMS( m/z( (rel(
intensity):(354((M+,(100);(HRMS((APCI):(calcd(for(C25H23O2([M(+(H]+(
355.1693,(found(355.1681.(
(
ꢀ 69Methoxy939methyl91,29diphenylnaphthalene( (5ba)( (Table( 2,(
Entry(2)(
(
ꢀ 29Methyl93,49diphenylphenanthlene((5ha)((Table(2,(Entry(8)(
Compound(5ha(was(obtained(according(to(the(general(procedure(
at(90(°C(in(66%(yield((0.0571(g,(0.17(mmol);(Yellow(solid;(m.p.(137B
140(°C;(1H(NMR((300(MHz,(CDCl3):(δ!(7.81B7.69((m,(4H),(7.38B7.33(
(m,(2H),(7.20B6.94((m,(11H),(2.23((s,(3H);(13C(NMR((75(MHz,(CDCl3):(
δ( 143.1,( 142.1,( 141.0,( 138.9,( 134.9,( 133.5,( 132.8,( 131.0,( 130.7,(
130.2,(129.0,(128.5,(128.2,(127.8,(127.7,(127.4,(127.1,(127.0,(126.3,(
125.8,(125.4,(124.9,(21.6;(EIBMS(m/z((rel(intensity):(344((M+,(100);(
HRMS((APPI):(calcd(for(C27H20([M]+(344.1560,(found(344.1549.(
(
Compound(5ba(was(obtained(according(to(the(general(procedure(
at(90(°C(in(57%(yield((0.0459(g,(0.14(mmol);(Yellow(solid;(m.p.(118B
120(°C;(1H(NMR((300(MHz,(CDCl3):(δ(7.67((s,(1H),(7.38((d,(J(=(9.2(Hz,(
1H),( 7.22B6.96( (m,( 12H),( 3.93( (s,( 3H),( 2.23( (s,( 3H);( 13C( NMR( (75(
MHz,( CDCl3):( δ( 157.5,( 140.6,( 139.5,( 138.5,( 137.7,( 135.0,( 134.1,(
130.9,( 130.3,( 128.5,( 127.44,( 127.36,( 126.7,( 126.4,( 126.3,( 126.0,(
117.7,(105.1,(55.3,(21.9;(EIBMS(m/z((rel(intensity):(324((M+,(100);(
HRMS((APPI):(calcd(for(C24H20O([M]+(324.1509,(found(324.1499.(
(
ꢀ 3,69Dimethyl91,29diphenylnaphthalene((5ca)((Table(2,(Entry(3)(
Compound(5ca(was(obtained(according(to(the(general(procedure(
at(100(°C(in(60%(yield((0.0464(g,(0.15(mmol);(Yellow(solid;(m.p.(
122B124(°C;(1H(NMR((300(MHz,(CDCl3):(δ(7.67((s,(1H),(7.60((s,(1H),(
7.36((d,(J(=(8.7(Hz,(1H),(7.24B7.00((m,(11H),(2.49((s,(3H),(2.23((d,(J(=(
0.6(Hz,(3H);(13C(NMR((75(MHz,(CDCl3):(δ(140.7,(139.5,(138.9,(138.3,(
135.3,(134.4,(133.1,(131.0,(130.2,(129.5,(127.5,(127.4,(127.3,(126.8,(
126.6,( 126.2,( 126.1,( 126.0,( 21.9,( 21.5;( EIBMS( m/z( (rel( intensity):(
308((M+,(100);(HRMS((APCI):(calcd(for(C24H21([M(+(H]+(309.1638,(
found(309.1628.(
ꢀ 39Cinnamyl91,29diphenylnaphthalene((5ia)((Table(2,(Entry(9)(
Compound(5ha(was(obtained(according(to(the(general(procedure(
at(90(°C(in(81%(yield((0.0752(g,(0.20(mmol);(Yellow(solid;(m.p.(153B
155(°C;(1H(NMR((300(MHz,(CDCl3):(δ(7.82((d,(J(=(8.0(Hz,(1H),(7.68((s,(
1H),( 7.48B7.42( (m,( 2H),( 7.35B7.30( (m,( 1H),( 7.22B7.07( (m,( 11H),(
6.97B6.89((m,(4H),(3.93((s,(2H);(13C(NMR((75(MHz,(CDCl3):(δ(140.8,(
139.9,(139.7,(139.3,(139.1,(137.4,(132.7,(131.5,(130.9,(130.4,(129.1,(
128.1,(127.9,(127.5,(127.4,(127.3((2C),(126.8,(126.3,(126.1,(125.8,(
125.6,(40.5;(EIBMS(m/z((rel(intensity):(370((M+,(100);(HRMS((APCI):(
calcd(for(C29H22([M]+(370.1716,(found(370.1705.(
(
(
ꢀ 1,29Bis(49methoxyphenyl)939methylnaphthalene((5ab)3a((Table(
2,(Entry(11)(
ꢀ
69Chloro939methyl91,29diphenylnaphthalene( (5da)( (Table( 2,(
Entry(4)(
Compound(5da(was(obtained(according(to(the(general(procedure(
at(90(°C(in(47%(yield((0.0385(g,(0.12(mmol);(White(solid;(m.p.(137B
138(°C;(1H(NMR((300(MHz,(CDCl3):(δ(7.80((d,(J(=(2.1(Hz,(1H),(7.67((s,(
1H),(7.40((d,(J(=(9.0(Hz,(1H),(7.24B6.99((m,(11H),(2.24((s,(3H);(13C(
NMR((75(MHz,(CDCl3):(δ(140.14,(140.11,(138.9,(138.7,(135.9,(133.5,(
131.5,( 130.9,( 130.0,( 129.6,( 128.6,( 127.6,( 127.5,( 126.53,( 126.50,(
126.3,(126.0,(125.6,(21.9;(EIBMS(m/z((rel(intensity):(328((M+,(100);(
HRMS((APPI):(calcd(for(C23H17Cl([M]+(328.1013,(found(328.1005.(
Compound(5ab(was(obtained(according(to(the(general(procedure(
at(100(°C(in(69%(yield((0.0603(g,(0.17(mmol);(Cream(solid;(m.p.(
201B202(°C;(1H(NMR((300(MHz,(CDCl3):(δ(7.82((d,(J!=(8.1(Hz,(1H),(
7.74((s,(1H),(7.50((d,(J!=(8.5(Hz,(1H),(7.44((td,(J!=(8.0,(1.1(Hz,(1H),(
7.30((ddd,(J!=(8.2,(7.6,(1.1(Hz,(1H),(7.02((dt,(J!=(8.7,(2.0(Hz,(2H),(
6.93((dt,(J!=(8.7,(2.8(Hz,(2H),(6.75((tt,(J!=(8.9,(2.8(Hz,(4H),(3.78((s,(
3H),(3.76((s,(3H),(2.25((s,(3H);(13C(NMR((75(MHz,(CDCl3):(δ!157.8,(
157.6,(139.8,(138.5,(134.9,(133.1,(132.8,(132.0,(131.8,(131.7,(131.1,(
4(|(J.!Name.,(2012,(00,(1B3(
This(journal(is(©(The(Royal(Society(of(Chemistry(20xx(
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Page 5 of 6
Organic & Biomolecular Chemistry
Please(do(not(adjust(margins(
Journal(Name(
(ARTICLE(
127.2,(127.0,(126.8,(125.6,(125.1,(113.0,(112.9,(55.1,(55.0,(22.0;(EIB
MS( m/z( (rel( intensity):( 354( (M+,( 100);( HRMS( (APCI):( calcd( for(
C25H22O2([M]+(354.1614,(found(354.1614.(
7.51B7.35((m,(5H),(7.27B7.18((m,(2H),(2.49((5aj’((minor))(and(2.37(
View Article Online
(5aj((major))((s,(3H),(2.15((5aj((major))(anDdO(2I:.1103.(1(053a9j’/(C(5mOinB0o1r9))5(9(sA,(
3H);(13C(NMR((75(MHz,(CDCl3):(δ(141.6((5aj( (major)),(140.4((5aj’(
(minor)),( 140.2( (5aj( (major)),( 138.3( (5aj’( (minor)),( 135.4( (5aj’(
(minor)),( 134.5( (5aj( (major)),( 133.1( (5aj’( (minor)),( 132.9( (5aj(
(major)),( 131.9( (5aj’( (minor)),( 131.7( (5aj’( (minor)),( 131.4( (5aj(
(major)),( 131.2( (5aj( (major)),( 130.2( (5aj’( (minor)),( 129.3( (5aj(
(major)),( 128.3,( 127.7( (5aj( (major)),( 127.1( (5aj’( (minor)),( 126.92(
(5aj’((minor)),(126.86((5aj’((minor)),(126.7((5aj((major)),(126.3((5aj’(
(minor)),( 125.8( (5aj( (major)),( 125.5( (5aj( (major)),( 125.2( (5aj(
(major)),( 124.83( (5aj’( (minor)),( 124.78( (5aj’( (minor)),( 124.4( (5aj(
(major)),(22.0((5aj((major)),(21.2((5aj’((minor)),(17.6((5aj’((minor)),(
16.5((5aj((major));(EIBMS(m/z((rel(intensity):(232((M+,(100).(
(
ꢀ 39Methyl91,29di9p9tolylnaphthalene((5ac)3a((Table(2,(Entry(12)(
Compound(5ac(was(obtained(according(to(the(general(procedure(
at(90(°C(in(50%(yield((0.0404(g,(0.13(mmol);(White(solid;(m.p.(159B
160(°C;(1H(NMR((300(MHz,(CDCl3):(δ(7.81((d,(J!=(8.1(Hz,(1H),(7.74((s,(
1H),(7.44((q,(J!=(7.0(Hz,(2H),(7.28((t,(J!=(7.1(Hz,(1H),(7.03B6.90((m,(
8H),( 2.30( (s,( 3H),( 2.27( (s,( 3H),( 2.23( (s,( 3H);( 13C( NMR( (75( MHz,(
CDCl3):( δ( 139.8,( 138.6,( 137.6,( 136.4,( 135.6,( 135.4,( 134.7,( 132.8,(
131.5,(130.8,(129.9,(128.2,(128.1,(127.2,(127.0,(126.8,(125.5,(125.1,(
22.0,(21.21,(21.18;(EIBMS(m/z((rel(intensity):(322((M+,(100);(HRMS(
(ESI):(calcd(for(C25H22Na([M(+(Na]+(345.1614,(found(345.1610.(
(
ꢀ 1,29Bis(49chlorophenyl)939methylnaphthalene( (5ad)( (Table( 2,(
Entry(13)(
Acknowledgements(
This work was supported by the COE Program in Chiba
University.
Compound(5ad(was(obtained(according(to(the(general(procedure(
at( 100( °C( in( 64%( yield( (0.0587( g,( 0.16( mmol);( White( solid;( m.p.(
166(°C;(1H(NMR((300(MHz,(CDCl3):(δ(7.84((d,(J!=(8.2(Hz,(1H),(7.77((s,(
1H),(7.50B7.31((m,(3H),(7.20((t,(J!=(6.4(Hz,(4H),(7.01((d,(J!=(4.6(Hz,(
2H),(6.95((d,(J!=(4.6(Hz,(2H),(2.23((s,(3H);(13C(NMR((75(MHz,(CDCl3):(
δ( 138.7,( 138.6,( 137.5,( 137.3,( 134.1,( 132.9,( 132.5,( 132.3,( 132.2,(
131.3,( 131.0,( 128.0,( 127.93,( 127.89,( 127.2,( 126.4,( 126.1,( 125.6,(
21.8;(EIBMS(m/z((rel(intensity):(362((M+,(88);(HRMS((APPI):(calcd(
for(C23H16Cl2([M]+(362.0624,(found(362.0623.(
Notes(and(references(
1
(a)(U.(Mitschke(and(P.(Bäuerle,(J.!Mater.!Chem.,!2000,(10,(
1471;( (b)( M.( D.( Watson,( A.( Fechtenkötter( and( K.( Müllen,(
Chem.!Rev.,!2001,(101,(1267;!(c)(M.(Bendikov(and(F.(Wudl,(
Chem.! Rev.,! 2004,( 104,( 4891;( (d)( J.( E.( Anthony,( Angew.!
Chem.!Int.!Ed.,!2008,(47,(452;((e)(I.(Kaur,(N.(N.(Stein,(R.(P.(
Kopreski( and( G.( P.( Miller,( J.! Am.! Chem.! Soc.,! 2008,( 131,!
3424;( (f)( J.( E.( Anthony,( A.( Facchetti,( M.( Heeney( and( S.( R.(
Marder,(Adv.!Mater.,!2010,(22,(3876.(
(
ꢀ 1,29Bis(49fluorophenyl)939methylnaphthalene( (5ae)( (Table( 2,(
Entry(14)(
Compound(5ae(was(obtained(according(to(the(general(procedure(
at( 100( °C( in( 65%( yield( (0.0537( g,( 0.16( mmol);( White( solid;( m.p.(
210(°C;(1H(NMR((300(MHz,(CDCl3):(δ(7.84((d,(J!=(8.1(Hz,(1H),(7.77((s,(
1H),(7.50B7.42((m,(2H),(7.33((t,(J!=(7.9(Hz,(1H),(7.06B6.86((m,(8H),(
2.24((s,(3H);(13C(NMR((75(MHz,(CDCl3):(δ(161.5((d,(J!=(245.5(Hz),(
161.3((d,(J!=(245.2(Hz),(139.1,(137.8,(136.3((d,(J!=(3.3(Hz),(135.1((d,(
J!=(3.3(Hz),(134.4,(133.0,(132.4((d,(J!=(7.8(Hz),(131.5((d,(J!=(7.8(Hz),(
131.3,( 127.7,( 127.2,( 126.5,( 125.9,( 125.5,( 114.8( (d,( J! =( 5.7( Hz),(
114.5((d,(J!=(5.8(Hz),(21.8;(EIBMS(m/z((rel(intensity):(330((M+,(100);(
HRMS((APPI):(calcd(for(C23H16F2([M]+(330.1215,(found(330.1211.(
(
2
3
H.(Zou,(L.(Zhou,(Y.(Li,(Y.(Cui,(H.(Zhong,(Z.(Pan,(Z.(Yanga(and(J.(
Quan,(J.!Med.!Chem.,!2010,(53,(994.(
(a)( Z.( Duan,( K.( Nakajima,( T.( Takahashi,( Chem.! Commun.,!
2001,( 1672;( (b)( C.( B.( Koning,( A.( L.( Rousseau( and( W.( A.( L.(
Otterlo,( Tetrahedron,! 2003,( 59,( 7;( (c)( S.( S.( Moleele,( J.( P.(
Michael(and(C.(B.(Koning,(Tetrahedron,!2006,(62,(2831;((d)(
A.(C.(Glass,(B.(B.(Morris,(L.(N.(Zakharov(and(S.BY.(Liu,(Org.!
Lett.,!2008,(10,(4855;((e)(A.(N.(Lowell,(M.(W.(Fennie(and(M.(
C.( Kozlowski,( J.! Org.! Chem.,! 2007,( 73,( 1911;( (f)( W.( A.( L.(
Otterlo(and(C.(B.(Koning,(Chem.!Rev.,!2009,(109,(3743;((g)(
S.BG.(Li,(X.BQ.(Hu,(Z.BX.(Jia(and(P.BF.(Xu,(Tetrahedron,!2010,(
66,(8557;((h)(H.(Xu,(S.(Li,(H.(Liu,(H.(Fu(and(Y.(Jiang,(Chem.!
Commun.,! 2010,( 46,( 7617;( (i)( K.( Sakabe,( H.( Tsurugi,( K.(
Hirano,(T.(Satoh(and(M.(Miura,(Chem.!Eur.!J.,!2010,(16,(445;(
(j)(D.(Mal,(A.(K.(Jana,(P.(Mitra(and(K.(Ghosh,(J.!Org.!Chem.,!
2011,(76,(3392;((k)(C.(C.(Malakar,(D.(Schmidt,(J.(Conrad(and(
U.( Beifuss,( Org.! Lett.,! 2011,( 13,( 1972;( (l)( J.BG.( Wang,( M.(
Wang,(J.BC.(Xiang,(Y.BP.(Zhu,(W.BJ.(Xue(and(A.BX.(Wu,(Org.!
Lett.,!2012,(14,(6060;((m)(A.(C.(Mantovani,(D.(F.(Back(and(G.(
Zeni,(Eur.!J.!Org.!Chem.,!2012,(4574;((n)(C.(C.(Malakar,(K.(
Sudheendran,( H.BG.( Imrich,( S.( Mika( and( U.( Beifuss,( Org.!
Biomol.!Chem.,!2012,(10,(3899;((o)(P.(Qian,(F.(Chen(and(C.(
Pan,(Synth.!Commun.,!2012,(42,(3242;((p)(R.(M.(Patel(and(N.(
P.(Argade,(Org!Lett.,!2013,(15,(14;((q)(K.(Sudheendran,(C.(C.(
Malakar,(J.(Conrad(and(U.(Beifuss,(Adv.!Synth.!Catal.,!2013,(
355,(2400;((r)(S.(Manojveer(and(R.(Balamurugan,(Org.!Lett.,!
2014,(16,(1712;((s)(Z.(Lou,(S.(Zhang,(C.(Chen,(X.(Pang,(M.(Li(
and(L.(Wen,(Adv.!Synth.!Catal.,!2014,(356,(153.(
ꢀ 39Methyl91,29dipropylnaphthalene((5ag)11((Table(2,(Entry(16)(
Compound(5ag(was(obtained(according(to(the(general(procedure(
at(100(°C(in(65%(yield((0.0366(g,(0.16(mmol);(Colorless(oil;(1H(NMR(
(300(MHz,(CDCl3):(δ(7.95((d,(J!=(8.1(Hz,(1H),(7.67((d,(J!=(9.3(Hz,(1H),(
7.49( (s,( 1H),( 7.43B7.33( (m,( 2H),( 3.05B3.00( (m,( 2H),( 2.78B2.73( (m,(
2H),(2.48((s,(3H),(1.72B1.53((m,(4H),(1.14B1.06((m,(6H);(13C(NMR((75(
MHz,( CDCl3):( δ( 137.4,( 135.7,( 134.9,( 132.4,( 131.0,( 127.7,( 126.8,(
124.8,(124.5,(123.9,(32.3,(30.9,(24.5,(23.8,(20.8,(14.9((2C);(EIBMS(
m/z((rel(intensity):(226((M+,(60).(
(
ꢀ
39Methyl91,29naphthalene( dimethanol,( 1,29diacetate( (5ai)(
(Table(2,(Entry(18)(
Compound(5ai(was(obtained(according(to(the(general(procedure(
at(100(°C(in(56%(yield((0.0399(g,(0.14(mmol);(White(solid;(m.p.(50B
51(°C;(1H(NMR((300(MHz,(CDCl3):(δ(8.09B8.05((m,(1H),(7.79B7.72((m,(
2H),(7.54B7.47((m,(2H),(5.72((s,(2H),(5.46((s,(2H),(2.57((s,(3H),(2.07(
(s,( 3H),( 2.06( (s,( 3H);( 13C( NMR( (75( MHz,( CDCl3):( δ( 170.9,( 170.7,(
135.2,(133.8,(132.9,(131.5,(131.2,(130.3,(127.8,(126.5,(126.3,(124.1,(
60.8,(59.7,(20.93,(20.89,(20.3;(EIBMS(m/z((rel(intensity):(286((M+,(
8);(HRMS((APPI):(calcd(for(C17H18O4Na([M(+(Na]+(309.1097,(found(
309.1097.(
(
ꢀ
1,39Dimethyl929phenylnaphthalene( (5aj)12( (including( 1,29
dimethyl939phenylnaphthalene((5aj’)13)((Table(2,(Entry(19)(
4
(a)(M.(A.(Bennett(and(E.(Wenger,(Organometallics,!1995,(14,(
1267;( (b)( D.( Peña,( D.( Pérez,( E.( ( Gutián,( L.( Casted,( J.! Am.!
Chem.!Sci.,!1999,(121,(5827B5828;((c)(T.(Yasukawa,(T.(Satoh,(
M( Miura( and( M.( Nomura,( J.! Am.! Chem.! Soc.,! 2002,( 124,(
12680;((d)(S.(Kawasaki,(T.(Satoh,(M.(Miura,(M.(Nomura,(J.!
The(mixture(of(5aj(and(5aj’(was(obtained(according(to(the(general(
procedure(at(110(°C(in(62%(yield((0.0536(g,(0.16(mmol)((5aj/5aj’(=(
9/1);(Colorless(oil;(1H(NMR((300(MHz,(CDCl3):(δ(8.02((m,(1H),(7.81B
7.74( (m,( 1H),( 7.66( (5aj’( (minor))( and( 7.60( (5aj( (major))( (s,( 1H),(
This(journal(is(©(The(Royal(Society(of(Chemistry(20xx!
J.!Name.,(2013,(00,(1B3(|(5(
Please(do(not(adjust(margins(

Please(do(not(adjust(margins(
Organic & Biomolecular Chemistry
Page 6 of 6
ARTICLE(
Org.! Chem.,! 2003,( 68,( 6836;( (e)( W.( Huang,( X.( Zhou,( K.(
Journal(Name(
and(X.(Fan,(Tetrahedron,(2013,(69,(5374;((j)(R.(VSi.e(wReArdticdley,O(Pnl.in(Ke.(
Prasad,(B.(B.(Ahuja(and(A.(Sudalai,(J.D!OOrI:g1.0!C.1h0e3m9/C.,!52O0B1031,9(5798A,(
5045;( (k)( Z.( Chen,( X.( Jia,( C.( Ye,( G.( Qiu( and( J.( Wu,( Chem.!
Asian.!J.,!2014,(9,(126.((
Kanno( and( T.( Takahashi,( Org.! Lett.,! 2004,( 6,( 2429;( (f)( K.(
Ueura,(T.(Satoh(and(M.(J.(Mura,!Org.!Chem.,!2007,(72,(5362;(
(g)(N.(Umeda,(H.(Tsurugi,(T.(Satoh(and(M.(Miura,(Angew.!
Chem.!Int.!Ed.,!2008,(47,(4019;((h)(Y.BT.(Wu,(K.BH.(Huang,(C.B
C.(Shin(and(T.BC.(Wu,(Chem.!Eur.!J.,!2008,(14,(6697;((i)(J.BC.(
Hsieh,(C.BH.(Cheng,(Chem.!Commun.,!2008,(2992;((j)(J.(Wu,(
W.(Cui,(X.(Mi,(Y.(Li(and(Y.(Wu,(Chem.!Commun.,!2010,(46,(
6771;((k)(T.(Fukutani,(K.(Hirano,(T.(Satoh(and(M.(Miura,(J.!
Org.!Chem.,!2011,(76,(2867;((l)(H.(Zhang,(X.(Cui,(X.(Yao,(J.(
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