Synthetic studies toward chiral aromatic triynes as key substrates for the asymmetric synthesis of helicene-like molecules

Article abstract of DOI:10.1135/cccc20042193

We have developed the synthesis of model nonracemic aromatic triynes (-)-(S)-1-4 containing the 1-{[2-(but-3-yn-1-yl)-1-naphthyl]ethynyl}-2-{[((S)-1- methylprop-2-yn-1-yl)oxy]-methyl}naphthalene unit. The common 1,2-di(2-substituted-1-naphthyl)acetylene p

Full text of DOI:10.1135/cccc20042193

Synthetic Studies Toward Chiral Aromatic Triynes
2193
SYNTHETIC STUDIES TOWARD CHIRAL AROMATIC TRIYNES AS
KEY SUBSTRATES FOR THE ASYMMETRIC SYNTHESIS OF
HELICENE-LIKE MOLECULES
1,
Zuzana ALEXANDROVÁ, Irena G. STARÁ *, Petr SEHNAL, Filip TEPLÝ,
2,
3
Ivo STARÝ *, David ŠAMAN and Pavel FIEDLER
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic,
1
Flemingovo nám. 2, 166 10 Prague 6, Czech Republic; e-mail: stara@uochb.cas.cz,
2
3
stary@uochb.cas.cz, saman@uochb.cas.cz
Received October 25, 2004
Accepted Novem ber 10, 2004
Dedicated to Professor Otto Exner on the occasion of his 80th birthday.
We h ave developed th e syn th esis of m odel n on racem ic arom atic triyn es (–)-(S)-1–4 con -
tain in g th e 1-{[2-(but-3-yn -1-yl)-1-n aph th yl]eth yn yl}-2-{[((S)-1-m eth ylprop-2-yn -1-yl)oxy]-
m eth yl}n aph th alen e un it. Th e com m on 1,2-di(2-substituted-1-n aph th yl)acetylen e part was
con structed via Son ogash ira couplin g of appropriate 1-iodon aph th alen es with 1-eth yn yl-
n aph th alen es both bearin g teth ered acetylen e un its in position s 2. Th e ch irality of triyn es
(–)-(S)-1–4 was in troduced by in corporatin g com m ercially available (–)-(S)-but-3-yn -2-ol (10)
in to teth ered acetylen e un its. Th e n on racem ic triyn es are in ten ded to be used as substrates
in stereoselective [2+2+2] triyn e cycloisom erization catalyzed by tran sition m etal com plexes.
Keyw ord s: Alkyn es; Aren es; Ch irality; Copper; Cross-couplin g; Helical structures; Palladium ;
Syn th esis design .
Asym m etric syn th esis of h elicen es an d related system s1 wh ich are in h er-
en tly ch iral is a ch allen gin g task n ot en tirely fulfilled so far. Differen t strat-
egies h ave em erged durin g th e last decades ran gin g from practical to curi-
ous. Th e m ost rem arkable ach ievem en ts were publish ed by Martin 2, Katz3,
Tan aka4, an d Carreñ o5 wh o successfully used ch iral auxiliaries, reactan ts or
reagen ts in th e stoich iom etric asym m etric syn th esis of h elicen es6. More-
over, we h ave recen tly disclosed basic prin ciples of th e altern ative catalytic
asym m etric syn th esis of h elicen e backbon es th at relies on in tram olecular
[2+2+2] cycloisom erization of triyn es un der catalysis with ch iral Ni(0) com -
plexes7. In spite of th ese sign ifican t ach ievem en ts8, th e resolution of
racem ates h as so far played a dom in an t role in producin g optically
en rich ed/pure h elicen es9.
Collect. Czech. Chem. Commun. (Vol. 69) (2004)
doi:10.1135/cccc20042193

2194
Alexandrová et al.:
It is obvious th at th e accessibility of n on racem ic h elicen es an d h elicen e-
like com poun ds via stoich iom etric asym m etric syn th esis h as n ot been fully
explored. To con trol h elicity of such system s, we h ave suggested th at
cen tral-to-h elical ch irality tran sfer m igh t be efficien t in [2+2+2] cycloiso-
m erization 10 of ch iral triyn es. Th us, we h ave design ed m odel triyn es 1–4
con tain in g an asym m etric carbon cen ter in th eir m olecules (Ch art 1). In
th is report, we describe th e syn th esis of such key arom atic triyn es. Th e de-
tailed study of diastereoselective [2+2+2] triyn e cycloisom erization , wh ich
is n ow un der way, will be publish ed separately11
.
R1
O
O
R1
R2
R2
(M,S) or (P,S)
Tol = p-tolyl
(-)-(S)-1, R1 = R2 = H
(-)-(S)-2, R1 = R2 = Tol
(-)-(S)-3, R1 = Tol, R2 = H
(-)-(S)-4, R1 = H, R2 = Tol
CHART 1
RESULTS AND DISCUSSION
Th e m odular syn th esis of ch iral triyn es (–)-(S)-1–4 was started from com -
m on buildin g blocks 5–13 (Ch art 2). Con cern in g n aph th yl derivatives, 5 is
com m ercially available an d th e preparation s of com poun ds 6 (lit.12), 7
(lit.7a), 8 (lit.7a), an d 9 (lit.7a) h ave recen tly been described by us in previous
R
R
TIPS
TIPS
Br
5, R = Br
6, R = I
7, R = Br
8, R = I
9
HO
HO
(a)
TMS
HO
12
13
(-)-(S)-10
(-)-(S)-11
CHART 2
(a) 4-Iodotoluen e (1.0 equiv.), [PdCl2(CH3CN)2] (0.8 m ole %), CuI (1.5 m ole %), PPh 3
(1.5 m ole %), diisopropylam in e (1.0 equiv.), toluen e, 0 °C to room tem perature, 3 h , 83%
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

Synthetic Studies Toward Chiral Aromatic Triynes
2195
papers. Both ch iral alkyn e (–)-(S)-10 an d its (R) en an tiom er are com m er-
cially available. Th e form er was routin ely tran sform ed to (–)-(S)-11 (lit.13)
usin g Pd(II)/Cu(I)-catalyzed Son ogash ira couplin g with 4-iodotoluen e. Th e
m on oprotected acetylen es 12 an d 13 are also com m ercially available.
Synthesis of Triynes (–)-(S)-1 and 2
We proposed altern ative syn th esis routes to get (–)-(S)-1 an d 2 (Sch em e 1).
First, we explored th e route startin g from readily available ben zylic brom ide
5 because th e con version to its coun terpart 6 requires th ree addition al
steps12. Com poun d 5 was treated with a sodium salt of optically pure
(–)-(S)-10 to give rise to (–)-(S)-14 in h igh yield. Th e subsequen t silylation
reaction with LDA/triisopropylsilyl ch loride led to (–)-(S)-15, again in h igh
TIPS
HO
(-)-(S)-10
9
R
O
Br
(f)
(d)
I
I
6
(-)-(S)-16, R = H
(e)
(-)-(S)-17, R = TIPS
R
O
HO
(c)
R
(-)-(S)-10
R
O
Br
(a)
Br
Br
(-)-(S)-18, R = TIPS
(-)-(S)-1, R = H
(-)-(S)-2, R = Tol
5
(g)
(h)
(-)-(S)-14, R = H
(b)
(-)-(S)-15, R = TIPS
SCHEME 1
(a) (–)-(S)-10 (1.3 equiv.), NaH (1.3 equiv.), THF, 0 °C, 30 m in , th en 5 (1.0 equiv.), room
tem perature to 50 °C, 3 h , 96%; (b) LDA (1.1 equiv.), THF, –78 °C, 45 m in , th en TIPSCl
(1.1 equiv.), –78 °C to room tem perature, 1 h , 95%; (c) BuLi (1.0 equiv.), THF, –78 °C, 15 m in ,
th en I2 (1.1 equiv.), –78 °C, 1 h , 41%; (d) (–)-(S)-10 (1.6 equiv.), BuLi (1.7 equiv.), THF–DMSO,
–30 °C to –5 °C, 45 m in , th en 6 (1.0 equiv.), 40 °C, 3.5 h , 81%; (e) LDA (1.0 equiv.), THF,
–78 °C, 45 m in , th en TIPSCl (2.0 equiv.), –78 °C to room tem perature, overn igh t, 84%; (f) 9
(1.1 equiv.), [Pd(PPh 3)4] (5 m ole %), CuI (10 m ole %), diisopropylam in e, room tem perature,
1 h , 81%; (g) Bu4NF (2.4 equiv.), THF, room tem perature, 15 m in , 82%; (h ) 4-iodotoluen e (2.1
equiv.), [Pd(PPh 3)4] (10 m ole %), CuI (20 m ole %), diisopropylam in e, 80 °C, 30 m in , 82%
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

2196
Alexandrová et al.:
yield. Note, th e use of lith ium diisopropylam ide as a base was essen tial14
because sodium h ydride was in effective in th e reaction an d butyllith ium
preferred a brom in e/lith ium exch an ge to th e term in al acetylen e deproton -
ation . Th e Son ogash ira couplin g of (–)-(S)-15 with diyn e 9 un der
[Pd(PPh 3)4]/CuI catalysis in diisopropylam in e did n ot proceed an d, th ere-
fore, we decided to con vert n aph th yl brom ide (–)-(S)-15 to a m ore reactive
n aph th yl iodide (–)-(S)-17. A routin e lith iation /iodin ation protocol allowed
us to produce (–)-(S)-17 but on ly in m oderate yield as th e m ajor iodide was
accom pan ied by n um erous side products. Th erefore, we took ben zylic bro-
m ide 6 as a startin g m aterial th at un derwen t sm ooth reaction with a so-
dium salt of (–)-(S)-10 to furn ish (–)-(S)-16 in good yield. Th e subsequen t
silylation with triisopropylsilyl ch loride in th e presen ce of lith ium diiso-
propylam ide afforded (–)-(S)-17 in h igh yield. Th en , th e Son ogash ira cou-
plin g of n aph th yl iodide (–)-(S)-17 with diyn e 9 proceeded sm ooth ly to fur-
n ish silylated triyn e (–)-(S)-18 in good yield. Desilylation with tetra-
butylam m on ium fluoride produced m odel un protected triyn e (–)-(S)-1 in
good yield. On reaction of (–)-(S)-1 with 4-iodotoluen e un der Pd(0)/Cu(I)
catalysis, double Son ogash ira couplin g took place to give, in h igh yield,
an oth er m odel triyn e (–)-(S)-2 with two teth ered acetylen e un its capped
with p-tolyl groups.
Synthesis of Triyne (–)-(S)-3
Th e critical step for th e successful preparation of triyn e (–)-(S)-3 was th e as-
sem bly of th e core din aph th ylacetylen e un it (Sch em e 2). Th e reaction of
th e ben zylic brom ide 6 with a sodium salt of (–)-(S)-11 furn ish ed (–)-(S)-19
in good yield. Th e subsequen t couplin g of (–)-(S)-19 with diyn e 9 in
diisopropylam in e un der [Pd(PPh 3)4]/CuI catalysis, h owever, yielded a com -
plex product m ixture in stead of th e expected (–)-(S)-22. Th erefore, we at-
tem pted to build th e din aph th ylacetylen e un it in a com plem en tary way.
Iodide (–)-(S)-19 reacted with (trim eth ylsilyl)acetylen e un der Pd(0)/Cu(I)
catalysis to produce (–)-(S)-20 in good yield. After sm ooth desilylation of
(–)-(S)-20 usin g sodium m eth oxide, diyn e (–)-(S)-21 was successfully cou-
pled with n aph th yl iodide 8 un der Pd(0)/Cu(I) catalysis to afford triyn e
(–)-(S)-22 in reason able yield. Th e fin al deprotection of (–)-(S)-22 with
tetrabutylam m on ium fluoride wh ich was n ot furth er optim ized, led to th e
desired triyn e (–)-(S)-3 in m oderate yield.
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

Synthetic Studies Toward Chiral Aromatic Triynes
2197
HO
Tol
(-)-(S)-11
Tol
O
Br
(a)
I
I
(b)
6
(-)-(S)-19
I
TIPS
Tol
O
Tol
8
O
R
(d)
R
(-)-(S)-22, R = TIPS
(-)-(S)-3, R = H
(-)-(S)-20, R = TMS
(-)-(S)-21, R = H
(e)
(c)
SCHEME 2
(a) (–)-(S)-11 (1.5 equiv.), BuLi (1.5 equiv.), THF–DMSO, –30 to 0 °C, 10 m in , th en
6
(1.0 equiv.), 40 °C, 16 h , 66%; (b) TMSC≡CH (1.2 equiv.), [Pd(PPh 3)4] (5 m ole %), CuI
(10 m ole %), diisopropylam in e, 80 °C, 2 h , 81%; (c) CH3ONa (1.7 equiv.), m eth an ol, room
tem perature, 1 h , 81%; (d) 8 (1.1 equiv.), [Pd(PPh 3)4] (5 m ole %), CuI (10 m ole %), diiso-
propylam in e, room tem perature, 1 h , 58%; (e) Bu4NF (2.4 equiv.), THF, room tem perature,
30 m in , 35%
Synthesis of Triyne (–)-(S)-4
Th e first attem pts at syn th esizin g (–)-(S)-4 started from th e readily available
buildin g block 7 (Sch em e 3). To cap th e teth ered acetylen e un it with a
p-tolyl group, alkyn e 7 was quan titatively desilylated with tetrabutyl-
am m on ium fluoride an d un protected alkyn e 23 reacted with 4-iodotoluen e
un der Pd(0)/Cu(I) catalysis to selectively produce 24 in n early quan titative
yield. Note, n o form ation of oligom eric products origin atin g from th e
self-couplin g of 23 was observed, as aryl brom ides are gen erally m uch less
reactive th an aryl iodides in Son ogash ira couplin g-type reaction s. In order
to en sure clean subsequen t couplin g with (trim eth ylsilyl)acetylen e, bro-
m ide 24 was tran sform ed via routin e lith iation /iodin ation in to iodide 25 in
excellen t yield. To our dism ay, h owever, couplin g of 25 with (trim eth yl-
silyl)acetylen e un der [Pd(PPh 3)4]/CuI catalysis in diisopropylam in e yielded
a com plex product m ixture th at precluded th e syn th esis of 29 via such
a route. We reason ed th e teth ered acetylen e un it capped with th e tolyl
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

2198
Alexandrová et al.:
group was reactive en ough to participate in th e un desirable in tram olecular
Heck-type addition . Th erefore, we decided to in terch an ge th e in troduction
of th e p-tolyl group an d eth yn yl on e. First, takin g advan tage of th e triiso-
propylsilyl group bulkin ess an d th e un reactivity of th e adjacen t teth ered
acetylen e un it, we successfully coupled iodide 8 with acetylen e 13 un der
Pd(0)/Cu(I) catalysis to furn ish orth ogon ally protected diyn e 26 in h igh
OH
OH
TIPS
R
Tol
I
13
OH
(f)
(d)
8
26, R = TIPS
27, R = H
28
(g)
(e)
R
Tol
Tol
Br
R
12
TMS
(b)
7, R = TIPS
23, R = H
24, R = Br
25, R = I
29
(c)
(a)
TIPS
R
O
O
I
(-)-(S) -17
Tol
(h)
(-)-(S)-30, R = TIPS
(-)-(S)-4, R = H
(i)
SCHEME 3
(a) Bu4NF (1.1 equiv.), THF, room tem perature, 15 m in , 99%; (b) 4-Iodotoluen e (1.0 equiv.),
[Pd(PPh 3)4] (5 m ole %), CuI (10 m ole %), diisopropylam in e, room tem perature, 2 h , 97%;
(c) BuLi (1.0 equiv.), THF, –78 °C, 15 m in , th en I2 (1.1 equiv.), –78 °C, 1 h , 93%; (d) 13
(3.6 equiv.), [Pd(PPh 3)4] (5 m ole %), CuI (10 m ole %), diisopropylam in e, 80 °C, 2 h , 86%;
(e) Bu4NF (3.3 equiv.), THF, room tem perature, 45 m in , 74%; (f) 4-iodotoluen e (1.1 equiv.),
[Pd(PPh 3)4] (5 m ole %), CuI (10 m ole %), diisopropylam in e, room tem perature, 30 m in , 78%;
(g) NaH (2.5 equiv.), toluen e, 110 °C, 40 m in , 78%; (h ) (–)-(S)-17 (1.0 equiv.), [Pd(PPh 3)4] (5
m ole %), CuI (10 m ole %), diisopropylam in e, room tem perature, 1 h , th en 80 °C, 2 h , 76%; (i)
Bu4NF (1.1 equiv.), THF, room tem perature, 10 m in , 84%
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

Synthetic Studies Toward Chiral Aromatic Triynes
2199
yield. Th en , by reactin g with tetrabutylam m on ium fluoride, we selectively
rem oved th e triisopropylsilyl group to produce m on oprotected diyn e 27 in
good yield. Th e subsequen t couplin g of 27 with 4-iodotoluen e un der
Pd(0)/Cu(I) catalysis proceeded sm ooth ly to give diyn e 28 with a capped
teth ered acetylen e un it in good yield. Th e 2-(2-h ydroxypropyl) protectin g
group was rem oved by treatin g of 28 with sodium h ydride to produce diyn e
29 in good yield. Son ogash ira couplin g of 29 with (–)-(S)-17 un der
Pd(0)/Cu(I) catalysis allowed us to assem ble triyn e (–)-(S)-30 in good yield.
Th e preparation of (–)-(S)-4 was fin alized by desilylation of (–)-(S)-30 with
tetrabutylam m on ium fluoride th at delivered th e target in h igh yield.
CONCLUSION
We h ave developed th e syn th esis of a series of m odel n on racem ic arom atic
triyn es (–)-(S)-1–4. Th eir successful preparation h as ben efited from th e m o-
dular ch aracter of th e gen eral syn th esis sch em e an d th e variability of th e
approach es explored. Th e com m on core 1,2-di(2-substituted-1-n aph th yl)-
acetylen e un it was con structed via Son ogash ira couplin g of 1-iodo-
n aph th alen es with 1-eth yn yln aph th alen es both bearin g teth ered acetylen e
un its in position s 2. Th e ch irality of triyn es (–)-(S)-1–4 was easily in tro-
duced by in corporatin g com m ercially available (–)-(S)-but-3-yn -2-ol (10)
in to th e teth ered acetylen e un its. Th e n on racem ic triyn es (–)-(S)-1–4 are in -
ten ded to be used as key substrates for stereoselective [2+2+2] triyn e
cycloisom erization catalyzed by tran sition m etal com plexes. Th is study is
un der way an d will be publish ed separately.
EXPERIMENTAL
Gen eral
1H NMR spectra were m easured at 499.8 or 500.13 MHz, 13C NMR spectra at 125.7 MHz, in
CDCl3 with TMS as an in tern al stan dard. Ch em ical sh ifts are given in ppm (δ-scale), cou-
plin g con stan ts (J) are given in Hz. HMBC experim en ts were set up for JC-H = 5 Hz. For cor-
rect assign m en t of both 1H an d 13C NMR spectra of key com poun ds, COSY, ROESY, HMQC,
HMBC, an d CIGAR-HMBC experim en ts were perform ed. For all th e oth er com poun ds, th e
gen eral sem iem pirical equation s were used for th e ch em ical sh ift assign m en t. IR spectra
(in cm –1) were m easured in CHCl3. EI MS spectra were determ in ed at an ion izin g voltage of
70 eV, m/z values are given alon g with th eir relative in ten sities (%). FAB MS spectra were
m easured usin g th e th ioglycerol-glycerol 3:1 m atrix, m/z values are given . HR MS spectra
were obtain ed by th e EI or APCI. Optical rotation s (in 10–1 deg cm 3 g–1) were m easured in
CH2Cl2. Com m ercially available reagen t-grade m aterials were used as received. Diiso-
propylam in e was degassed by th ree freeze-pum p-th aw cycles before use; dim eth yl sulfoxide
was distilled from calcium h ydride in vacuo; m eth an ol was distilled from sodium un der
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

2200
Alexandrová et al.:
argon ; THF was fresh ly distilled from sodium /ben zoph en on e un der n itrogen ; toluen e was
distilled from calcium h ydride un der argon . TLC was perform ed on Silica gel 60 F254-coated
alum in ium sh eets (Merck) an d spots were detected with a solution of Ce(SO4)2·4H2O (1%)
an d H3P(Mo3O10
)
(2%) in sulfuric acid (10%). Flash ch rom atograph y was perform ed on
4
Silica gel 60 (0.040–0.063 m m or <0.063 m m , Merck) or on Biotage KP-Sil Silica cartridges
(0.040–0.063 m m ) used in Horizon HPFC system (Biotage, In c.).
1-{[2-(But-3-yn -1-yl)-1-n aph th yl]eth yn yl}-2-{[((S)-1-m eth ylprop-2-yn -1-yl)oxy]m eth yl}-
n aph th alen e (1)
Tetrabutylam m on ium fluoride (1
M solution in tetrah ydrofuran , 2.17 m l, 2.34 m m ol,
2.40 equiv.) was added to silylated triyn e (–)-(S)-18 (700 m g, 0.960 m m ol) in tetrah ydro-
furan (20 m l) un der argon . Th e m ixture was stirred at room tem perature for 15 m in . Th e
solven t was evaporated in vacuo an d th e residue was ch rom atograph ed on silica gel (petro-
leum eth er–eth er 100:0 to 95:5) to afford un protected triyn e (–)-(S)-1 (323 m g, 82%) as an
oil. 1H NMR: 1.56 (3 H, d, J = 6.6); 2.03 (1 H, t, J = 2.7); 2.43 (1 H, d, J = 2.1); 2.75 (2 H, dt,
J = 7.7, 7.7, 2.7); 3.65 (2 H, t, J = 7.7); 4.41 (1 H, dq, J = 6.6, 6.6, 6.6, 2.1); 5.19 (1 H, d, J =
12.6); 5.35 (1 H, d, J = 12.6); 7.51 (1 H, d, J = 8.4); 7.52 (1 H, ddd, J = 8.1, 6.8, 1.2); 7.55
(1 H, ddd, J = 8.1, 6.8, 1.2); 7.62 (1 H, ddd, J = 8.4, 6.8, 1.4); 7.64 (1 H, ddd, J = 8.4, 6.8,
1.4); 7.74 (1 H, d, J = 8.5); 7.84 (1 H, dd, J = 8.4, 0.8); 7.87 (1 H, ddt, J = 8.2, 1.4, 0.8, 0.8);
7.89 (1 H, ddt, J = 8.1, 1.4, 0.6, 0.6); 7.90 (1 H, dt, J = 8.5, 0.6, 0.6); 8.59 (1 H, dq, J = 8.4,
0.9, 0.9, 0.9); 8.62 (1 H, ddt, J = 8.4, 1.2, 0.9, 0.9). 13C NMR: 20.04 (t), 22.15 (q), 34.70 (t),
65.00 (d), 69.28 (s), 69.43 (t), 73.46 (d), 83.70 (s), 83.72 (s), 94.30 (s), 95.91 (s), 119.07 (s),
119.60 (s), 125.40 (d), 125.98 (d), 126.27 (d), 126.33 (d), 126.42 (d), 127.07 (d), 127.18 (d),
127.35 (d), 128.22 (d), 128.29 (d), 128.77 (d), 128.71 (d), 132.10 (s), 132.69 (s), 133.42 (s),
133.71 (s), 138.80 (s), 141.36 (s). IR: 3307 vs, 3060 m , 2190 vw, 2118 w, 1621 w, 1593 w,
1570 w, 1508 m , 1375 w, 1261 w, 1098 s, 867 w, 820 s, 638 s. EI MS: 412 (M• +, 100), 385
(12), 368 (10), 359 (32), 341 (31), 331 (37), 319 (51), 315 (41), 302 (40), 289 (71), 276 (29),
257 (8), 239 (7), 215 (9), 203 (15), 191 (47), 179 (20), 165 (40), 151 (36), 141 (38), 125 (13),
115 (15), 97 (28), 83 (31), 69 (37), 57 (61), 43 (66). HR EI MS: calculated for C31H24
412.1827; foun d 412.1807. [α ]2D2 –57 (c 0.45).
O
2-{[((S)-1-Methyl-3-p-tolylprop-2-yn-1-yl)oxy]m ethyl}-1-{[2-(4-p-tolylbut-3-yn-1-yl)-1-naphthyl]-
eth yn yl}n aph th alen e (2)
A Sch len k flask was ch arged with [Pd(PPh 3)4] (10 m g, 0.009 m m ol, 10 m ole %), CuI (3 m g,
0.0016 m m ol, 20 m ole %), 4-iodotoluen e (38 m g, 0.174 m m ol, 2.10 equiv.), an d flush ed
with argon . Alkyn e 1 (34 m g, 0.082 m m ol) in diisopropylam in e (3 m l) was added an d th e
m ixture was stirred at 80 °C for 30 m in . Volatiles were rem oved in vacuo an d th e residue
was ch rom atograph ed on silica gel (h exan es–eth er 95:5) to afford 2 (40 m g, 82%) as an
am orph ous solid. M.p. 156 °C (petroleum eth er–eth er). 1H NMR: 1.60 (3 H, d, J = 6.6); 2.26
(3 H, brs); 2.31 (3 H, brs); 2.92 (2 H, t, J = 7.7); 3.48 (2 H, t, J = 7.5); 4.61 (1 H, q, J = 6.6);
5.28 (1 H, d, J = 12.7); 5.40 (1 H, d, J = 12.7); 6.91 (2 H, m ); 7.04 (2 H, m ); 7.15 (2 H, m );
7.23 (2 H, m ); 7.48 (1 H, ddd, J = 8.1, 6.8, 1.2); 7.51 (1 H, d, J = 8.5); 7.52 (1 H, ddd, J = 8.0,
6.8, 1.2); 7.56 (1 H, ddd, J = 8.3, 6.8, 1.4); 7.60 (1 H, ddd, J = 8.3, 6.8, 1.4); 7.78 (1 H, d, J =
8.5); 7.82 (1 H, dd, J = 8.5, 0.7); 7.85 (1 H, ddt, J = 8.0, 1.4, 0.6, 0.6); 7.88 (1 H, ddt, J = 8.1,
1.4, 0.6, 0.6); 7.90 (1 H, dd, J = 8.5, 0.7); 8.63 (2 H, dt, J = 8.3, 1.0, 1.0). 13C NMR: 21.08 (t),
21.38 (2 × q), 22.35 (q), 35.02 (t), 65.69 (d), 69.42 (t), 81.63 (s), 85.63 (s), 88.32 (s),
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

Synthetic Studies Toward Chiral Aromatic Triynes
2201
88.61 (s), 94.28 (s), 95.98 (s), 119.22 (s), 119.51 (s), 119.60 (s), 120.78 (s), 125.59 (d),
125.85 (d), 126.26 (d), 126.31 (d), 126.34 (d), 127.06 (d), 127.15 (d), 127.53 (d), 128.10 (d),
128.23 (d), 128.50 (d), 128.69 (d), 128.78 (d), 128.89 (d), 131.42 (d), 131.54 (d), 132.07 (s),
132.68 (s), 133.75 (2 × s), 137.51 (s), 138.11 (s), 139.09 (s), 141.74 (s). IR: 3059 m , 3011 s, 2226
w, 2203 vw (sh ), 1620 w, 1610 w, 1593 m , 1570 m , 1510 vvs, 1399 s, 1373 m , 1328 s, 1260 m,
1180 w, 1094 vs, 1022 m, 867 m, 819 vvs. EI MS: 592 (M•+, 0.2), 496 (0.4), 467 (0.3), 449 (66), 421
(25), 289 (20), 143 (40), 129 (50), 97 (40), 91 (32), 83 (48), 73 (70), 57 (96), 43 (100). HR APCI MS:
calculated for C45H37O (M•+ + 1) 593.2844; found 593.2855. [α ]2D2 –80 (c 0.15).
1-{[2-(But-3-yn -1-yl)-1-n aph th yl]eth yn yl}-2-{[((S)-1-m eth yl-3-p-tolylprop-2-yn -1-yl)oxy]-
m eth yl}n aph th alen e (3)
Tetrabutylam m on ium fluoride (1
M solution in tetrah ydrofuran , 350 µl, 0.380 m m ol,
2.40 equiv.) was added to silylated triyn e (–)-(S)-22 (100 m g, 0.160 m m ol) in tetrah ydro-
furan (3 m l) un der argon . Th e m ixture was stirred at room tem perature for 30 m in . Th e sol-
ven t was evaporated in vacuo an d th e residue was ch rom atograph ed on silica gel (petroleum
eth er–eth er 98:2) to afford un protected triyn e (–)-(S)-3 (27 m g, 35%) as an oil. 1H NMR: 1.62
(3 H, d, J = 6.6); 2.01 (1 H, t, J = 2.6); 2.28 (3 H, s); 2.71 (2 H, dt, J = 7.6, 7.6, 2.6); 3.71 (2 H,
t, J = 7.6); 4.62 (1 H, d, J = 6.6); 5.28 (1 H, d, J = 12.8); 5.39 (1 H, d, J = 12.8); 6.91 (2 H, m );
7.14 (2 H, m ); 7.46 (1 H, d, J = 8.4); 7.48 (1 H, ddd, J = 8.1, 6.8, 1.2); 7.55 (1 H, ddd, J = 8.1,
6.8, 1.2); 7.55 (1 H, ddd, J = 8.4, 6.8, 1.4); 7.64 (1 H, ddd, J = 8.4, 6.8, 1.4); 7.79 (1 H, d, J =
8.5); 7.82 (1 H, brd, J = 8.4); 7.85 (1 H, brdd, J = 8.1, 1.4); 7.89 (1 H, brdd, J = 8.1, 1.4); 7.91
(1 H, brd, J = 8.5); 8.60 (1 H, brdd, J = 8.4, 1.2); 8.62 (1 H, brdd, J = 8.4, 1.2). 13C NMR:
19.99 (t), 21.39 (q), 22.37 (q), 34.66 (t), 65.69 (d), 69.22 (d), 69.41 (t), 83.71 (s), 85.64 (s),
88.30 (s), 94.38 (s), 95.82 (s), 119.18 (s), 119.50 (s), 119.61 (s), 125.63 (d), 125.92 (d),
126.29 (d), 126.31 (d), 126.32 (d), 127.12 (d), 127.13 (d), 127.29 (d), 128.11 (d), 128.28 (d),
128.59 (d), 128.74 (d), 128.79 (d), 131.53 (d), 132.09 (s), 132.70 (s), 133.45 (s), 133.75 (s),
138.14 (s), 139.11 (s), 141.36 (s). IR: 3308 m , 3059 m , 2226 w, 2195 vw (sh ), 2118 w,
1620 vw, 1608 vw, 1593 w, 1570 w, 1510 s, 1328 m , 1260 w, 1127 m (sh ), 1105 s (sh ),
1094 s, 1075 m , 1022 m , 867 w, 819 vs, 640 m , 524 w, 428 w. EI MS: 502 (M• +, 7), 487 (15),
459 (32), 449 (14), 406 (5), 368 (6), 359 (21), 341 (29), 331 (31), 315 (40), 302 (44), 289
(65), 276 (23), 265 (7), 231 (8), 203 (13), 191 (68), 165 (34), 153 (15), 141 (61), 128 (100),
115 (40), 105 (11), 91 (17), 65 (8), 55 (11), 43 (53). HR EI MS: calculated for C38H30
502.2297; foun d 502.2278. [α ]2D2 –108 (c 0.08).
O
1-{[2-(4-p-Tolylbut-3-yn -1-yl)-1-n aph th yl]eth yn yl}-2-{[((S)-1-m eth ylprop-2-yn -1-yl)oxy]-
m eth yl}n aph th alen e (4)
Tetrabutylam m on ium fluoride (1
M solution in tetrah ydrofuran , 95 µl, 0.100 m m ol,
1.10 equiv.) was added to silylated triyn e (–)-(S)-30 (60 m g, 0.090 m m ol) in tetrah ydrofuran
(3 m l) un der argon . Th e m ixture was stirred at room tem perature for 10 m in . Th e solven t
was evaporated in vacuo an d th e residue was ch rom atograph ed on silica gel (petroleum
eth er–eth er 93:7) to afford un protected triyn e (–)-(S)-4 (39 m g, 84%) as an oil. 1H NMR: 1.54
(3 H, d, J = 6.6); 2.32 (3 H, s); 2.42 (1 H, d, J = 2.0); 2.95 (2 H, t, J = 7.5); 3.53 (2 H, t, J =
7.5); 4.40 (1 H, dq, J = 6.6, 6.6, 6.6, 2.0); 5.20 (1 H, d, J = 12.6); 5.36 (1 H, d, J = 12.6); 7.05
(2 H, m ); 7.24 (2 H, m ); 7.52 (1 H, ddd, J = 8.1, 6.8, 1.2); 7.53 (1 H, ddd, J = 8.1, 6.8, 1.2);
7.56 (1 H, d, J = 8.4); 7.61 (1 H, ddd, J = 8.4, 6.8, 1.4); 7.62 (1 H, ddd, J = 8.4, 6.8, 1.4); 7.74
(1 H, d, J = 8.5); 7.85 (1 H, brd, J = 8.4); 7.88 (1 H, brdd, J = 8.1, 1.4); 7.88 (1 H, brdd, J =
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

2202
Alexandrová et al.:
8.1, 1.4); 7.89 (1 H, brd, J = 8.5); 8.63 (1 H, ddt, J = 8.4, 1.0, 0.8, 0.8); 8.64 (1 H, ddt, J = 8.4,
1.0, 0.8, 0.8). 13C NMR: 21.13 (t), 21.38 (q), 22.13 (q), 35.08 (t), 65.01 (d), 69.43 (t),
73.46 (d), 81.68 (s), 83.73 (s), 88.57 (s), 94.21 (s), 96.08 (s), 119.12 (s), 119.62 (s), 120.75 (s),
125.37 (d), 125.92 (d), 126.31 (d), 126.31 (d), 126.42 (d), 127.02 (d), 127.20 (d), 127.57 (d),
128.21 (d), 128.25 (d), 128.62 (d), 128.72 (d), 128.91 (d), 131.43 (d), 132.10 (s), 132.68 (s),
133.43 (s), 133.74 (s), 137.56 (s), 138.80 (s), 141.74 (s). IR: 3307 m , 3060 w, 2225 vw,
2196 vw, 2112 vw, 1620 vw, 1593 w, 1571 w, 1510 s, 1452 w, 1431 w, 1399 m , 1375 w,
1326 m , 1313 w, 1275 w, 1264 w (sh ), 1181 w, 1146 w (sh ), 1135 w (sh ), 1110 s (sh ), 1098 s,
1063 m , 1040 w, 1023 w, 867 w, 819 vs, 638 m , 530 w, 427 w. EI MS: 502 (M• +, 4), 487 (15),
459 (4), 449 (79), 434 (8), 421 (100), 411 (28), 393 (7), 357 (11), 339 (19), 329 (26), 315
(23), 302 (41), 289 (79), 276 (30), 265 (13), 255 (19), 191 (8), 165 (23), 155 (15), 141 (70),
129 (38), 119 (24), 105 (27), 83 (18), 69 (25), 57 (37), 53 (20), 43 (37). HR EI MS: calculated
for C38H30O 502.2297; foun d 502.2306. [α ]2D2 –58 (c 0.11).
(S)-4-(4-Meth ylph en yl)but-3-yn -2-ol (11)
A m odified procedure was used13: A Sch len k flask was ch arged with 4-iodotoluen e (1.50 g,
6.88 m m ol, 1.00 equiv.), [PdCl2(CH3CN)2] (14 m g, 0.060 m m ol, 0.8 m ole %), CuI (20 m g,
0.100 m m ol, 1.5 m ole %), triph en ylph osph in e (28 m g, 0.110 m m ol, 1.5 m ole %), an d
flush ed with argon . Toluen e (7 m l) was added, th e m ixture was cooled to 0 °C, an d
propargylic alcoh ol (–)-(S)-10 (540 µl, 6.88 m m ol) in degassed diisopropylam in e (970 µl,
6.90 m m ol, 1.00 equiv.) was added. Th e m ixture was stirred at 0 °C for 5 m in an d th en at
room tem perature for 3 h . Volatiles were rem oved in vacuo an d th e residue was extracted
with eth er. Th e solven t was rem oved in vacuo an d th e residue was ch rom atograph ed on
silica gel (h exan es) to afford (–)-(S)-11 (910 m g, 83%) as an oil. 1H NMR, 13C NMR, an d IR
spectra were in agreem en t with th e literature data13. [α ]D22 –27 (c 0.13).
1-Brom o-2-{[((S)-1-m eth ylprop-2-yn -1-yl)oxy]m eth yl}n aph th alen e (14)
A Sch len k flask was ch arged with NaH (80% suspen sion in m in eral oil, 250 m g, 8.33 m m ol,
1.25 equiv.), flush ed with argon , an d h ydride was wash ed with h exan e (3×). THF (40 m l)
was added an d th e m ixture was cooled to 0 °C. Alcoh ol (–)-(S)-10 (675 µl, 8.54 m m ol,
1.30 equiv.) was added an d th e m ixture was stirred at 0 °C for 30 m in . Brom ide 5 (2 g,
6.67 m m ol) in THF (40 m l) was added an d th e m ixture was stirred at room tem perature for
1 h an d th en at 50 °C for 2 h . Th e solven t was evaporated in vacuo an d th e residue was par-
tition ed between eth er an d water. Organ ic layer was separated, wash ed with water (3×), an d
dried over an h ydrous Na2SO4. Th e solven t was rem oved in vacuo to afford (–)-(S)-14 (1.86 g,
96%) as an oil. 1H NMR: 1.55 (3 H, d, J = 6.6); 2.50 (1 H, d, J = 2.1); 4.33 (1 H, dq, J = 6.6,
6.6, 6.6, 2.1); 4.87 (1 H, d, J = 12.8); 5.05 (1 H, d, J = 12.8); 7.51 (1 H, ddd, J = 8.1, 6.8, 1.2);
7.59 (1 H, ddd, J = 8.5, 6.8, 1.3); 7.63 (1 H, brd, J = 8.4); 7.81 (1 H, ddd, J = 8.4, 0.8, 0.6);
7.82 (1 H, ddt, J = 8.1, 1.3, 0.7, 0.7); 8.32 (1 H, ddt, J = 8.5, 1.2, 0.7, 0.7). 13C NMR: 22.08
(q), 65.14 (d), 70.80 (t), 73.38 (d), 83.59 (s), 122.74 (s), 126.25 (d), 126.45 (d), 127.10 (d),
127.36 (d), 127.64 (d), 128.11 (d), 132.25 (s), 134.07 (s), 135.61 (s). IR: 3307 vs, 2113 w,
1625 w, 1599 w, 1559 m , 1503 s, 1259 s, 1112 vs, 1099 vs, 1032 m , 864 m , 818 vs, 666 s,
639 s. EI MS: 290 (M• + with 81Br, 30), 288 (M• + with 79Br, 30), 236 (21), 221 (33), 207 (5),
179 (17), 165 (23), 157 (14), 141 (100), 128 (79), 115 (5), 63 (6), 53 (16), 43 (11). HR EI MS:
calculated for C15H1381BrO 290.0129 an d for C15H1379BrO 288.0149; foun d 290.0115 an d
288.0122, respectively. [α ]2D2 –87 (c 0.10).
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

Synthetic Studies Toward Chiral Aromatic Triynes
2203
{(S)-3-[(1-Brom o-2-n aph th yl)m eth oxy]but-1-yn -1-yl}(triisopropyl)silan e (15)
Lith ium diisopropylam ide (2 M solution in tetrah ydrofuran , 2 m l, 4.0 m m ol, 1.10 equiv.)
was added to (–)-(S)-14 (1.62 g, 3.64 m m ol) in tetrah ydrofuran (40 m l) at –78 °C un der ar-
gon . Th e m ixture was stirred at –78 °C for 45 m in an d ch lorotriisopropylsilan e (0.85 m l,
4.0 m m ol, 1.10 equiv.) was added. Th e reaction m ixture was stirred at –78 °C for addition al
15 m in an d th en at room tem perature for 45 m in . Volatiles were rem oved in vacuo an d th e
residue was partition ed between dich lorom eth an e an d water. Th e organ ic layer was sepa-
rated, wash ed with water (3×), an d dried over an h ydrous Na2SO4. Th e solven t was rem oved
in vacuo to afford (–)-(S)-15 (2.60 g, 95%) as an oil. 1H NMR: 1.05–1.11 (21 H, m ); 1.53
(3 H, d, J = 6.6); 4.37 (1 H, q, J = 6.6); 4.90 (1 H, d, J = 13.0); 5.09 (1 H, d, J = 13.0); 7.51
(1 H, ddd, J = 8.1, 6.8, 1.2); 7.58 (1 H, ddd, J = 8.4, 6.8, 1.4); 7.64 (1 H, d, J = 8.5); 7.81 (1 H,
brd, J = 8.5); 7.82 (1 H, ddt, J = 8.1, 1.4, 0.6, 0.6); 8.32 (1 H, ddt, J = 8.4, 1.2, 0.9, 0.9).
13C NMR: 11.17 (d), 18.61 (q), 22.36 (q), 65.73 (d), 70.60 (t), 86.24 (s), 107.32 (s), 122.69 (s),
126.31 (d), 126.37 (d), 127.07 (d), 127.29 (d), 127.57 (d), 128.09 (d), 132.23 (s), 134.02 (s),
135.89 (s). IR: 3059 m , 2866 vs, 2165 m , 1623 w, 1599 m , 1558 m , 1503 s, 1463 vs, 1427 w,
1383 s, 1372 s, 1325 vs, 1258 s, 1115 vs (sh ), 1097 vs, 1071 vs, 997 s, 969 s, 884 vs, 865 s,
816 vs, 681 s, 660 s, 646 s, 532 s, 413 m . EI MS: 446 (M• + with 81Br, 12), 444 (M• + with 79Br,
12), 403 (62), 373 (39), 359 (8), 321 (15), 307 (23), 279 (55), 251 (6), 235 (18), 219 (100),
207 (10), 192 (31), 167 (21), 141 (52), 125 (24), 115 (12), 97 (17), 83 (23), 69 (16), 59 (20),
41 (9). HR EI MS: calculated for C24H3381BrOSi 446.1463 an d for C24H3379BrOSi 444.1484;
foun d 446.1481 an d 444.1470, respectively. [α ]2D2 –73 (c 0.20).
1-Iodo-2-{[((S)-1-m eth ylprop-2-yn -1-yl)oxy]m eth yl}n aph th alen e (16)
A Sch len k flask was ch arged with (–)-(S)-10 (1.60 m l, 20.32 m m ol, 1.60 equiv.) an d flush ed
with argon . Tetrah ydrofuran (30 m l) an d dim eth yl sulfoxide (5.7 m l) were added an d th e
solution was cooled to –30 °C. Th en butyllith ium (1.6 M solution , 2.40 m l, 3.89 m m ol,
1.70 equiv.) was added. Th e m ixture was stirred at –30 °C for 30 m in an d at –5 °C for
15 m in . Brom ide 6 (4.23 g, 12.20 m m ol) in tetrah ydrofuran (15 m l) was added an d th e reac-
tion m ixture was stirred at 40 °C for 3.5 h . Volatiles were rem oved in vacuo an d th e residue
was ch rom atograph ed on silica gel (petroleum eth er–eth er 99:1 to 97:3) to afford (–)-(S)-16
(3.32 g, 81%) as an oil. 1H NMR: 1.56 (3 H, d, J = 6.6); 2.51 (1 H, d, J = 2.1); 4.35 (1 H, dq,
J = 6.6, 6.6, 6.6, 2.1); 4.81 (1 H, d, J = 12.7); 5.03 (1 H, d, J = 12.7); 7.50 (1 H, ddd, J = 8.1,
6.9, 1.2); 7.57 (1 H, ddd, J = 8.5, 6.9, 1.5); 7.59 (1 H, d, J = 8.4); 7.77 (1 H, ddt, J = 8.1, 1.5,
0.5, 0.5); 7.81 (1 H, brdt, J = 8.4, 0.7, 0.7); 8.25 (1 H, ddt, J = 8.5, 1.2, 0.8, 0.8). 13C NMR:
22.07 (q), 65.12 (d), 73.47 (d), 76.03 (t), 83.55 (s), 103.44 (s), 126.27 (d), 126.50 (d),
127.71 (d), 128.28 (d), 128.74 (d), 132.33 (d), 133.73 (d), 134.72 (d), 139.66 (s). IR: 3306 s,
3059 m , 2112 w, 1621 w, 1596 w, 1552 m , 1502 s, 1374 m , 1257 s, 1113 vs (sh ), 1099 vvs,
1031 m , 863 m , 817 s, 638 s, 523 m . EI MS: 336 (M• +, 53), 306 (6), 282 (20), 267 (22), 179
(11), 165 (36), 141 (100), 128 (44), 115 (5), 83 (5), 53 (16), 43 (14). HR EI MS: calculated for
C
15H13IO 336.0011; foun d 336.0008. [α ]2D2 –75 (c 0.37).
{(S)-3-[(1-Iodo-2-n aph th yl)m eth oxy]but-1-yn -1-yl}(triisopropyl)silan e (17)
Method 1: Butyllith ium (1.6 M solution , 3.8 m l, 6.05 m m ol, 1.04 equiv.) was added to
(–)-(S)-15 (2.59 g, 5.81 m m ol) in tetrah ydrofuran (15 m l) at –78 °C un der argon . Th e m ix-
ture was stirred at –78 °C for 15 m in . Iodin e (1.62 g, 6.38 m m ol, 1.10 equiv.) in tetra-
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

2204
Alexandrová et al.:
h ydrofuran (10 m l) was added an d th e reaction m ixture was stirred at –78 °C for 1 h . Th e
solven t was evaporated in vacuo an d th e residue was partition ed between eth er an d water.
Th e organ ic layer was separated, wash ed with aqueous Na2S2O3 (3×), water (2×), an d dried
over an h ydrous Na2SO4. Volatiles were rem oved in vacuo an d th e residue was ch rom atog-
raph ed on silica gel (petroleum eth er–eth er 99.5:0.5) to afford iodide (–)-(S)-17 (1.17 g, 41%)
as an oil.
Method 2: Lith ium diisopropylam ide (2 M solution in tetrah ydrofuran , 670 µl, 1.34 m m ol,
1.04 equiv.) was added to (–)-(S)-16 (435 m g, 1.29 m m ol) in tetrah ydrofuran (6 m l) at
–78 °C un der argon . Th e m ixture was stirred at –78 °C for 45 m in an d ch lorotriisopropyl-
silan e (560 µl, 2.62 m m ol, 2.03 equiv.) was added. Th e reaction m ixture was stirred at
–78 °C to room tem perature overn igh t. Volatiles were rem oved in vacuo an d th e residue was
ch rom atograph ed on silica gel (petroleum eth er–eth er 100:0 to 98:2) to afford (–)-(S)-17
(535 m g, 84%) as an oil.
1H NMR: 1.07–1.12 (21 H, m ); 1.55 (3 H, d, J = 6.6); 4.38 (1 H, q, J = 6.6); 4.83 (1 H, d, J =
12.9); 5.06 (1 H, d, J = 12.9); 7.49 (1 H, ddd, J = 8.0, 6.8, 1.2); 7.56 (1 H, ddd, J = 8.5, 6.8,
1.4); 7.60 (1 H, d, J = 8.4); 7.76 (1 H, ddt, J = 8.0, 1.4, 0.7, 0.7); 7.80 (1 H, dt, J = 8.4, 0.6,
0.6); 8.24 (1 H, ddt, J = 8.5, 1.2, 0.7, 0.7). 13C NMR: 11.17 (d), 18.65 (q), 22.37 (q), 65.75 (d),
75.85 (t), 86.29 (s), 103.26 (s), 107.28 (s), 126.26 (d), 126.41 (d), 127.64 (d), 128.26 (d),
128.67 (d), 132.28 (d), 133.69 (s), 134.70 (s), 139.97 (s). IR: 3059 w, 2891 s, 2866 vvs,
2164 w, 1620 vw, 1596 vw, 1552 w, 1501 m , 1463 s, 1383 w, 1372 m , 1256 m , 1097 s,
1031 w, 997 m , 883 s, 863 w, 815 s, 679 s, 664 m , 523 w. EI MS: 492 (M• +, 27), 449 (87),
419 (12), 353 (15), 325 (13), 307 (8), 279 (68), 267 (100), 251 (9), 237 (6), 227 (17), 208 (8),
199 (19), 192 (42), 182 (7), 167 (17), 141 (56), 125 (22), 111 (19), 97 (14), 83 (19), 69 (15),
59 (21), 41 (10). FAB MS: 449, 353, 325, 307, 289, 279, 267, 165, 141, 125, 115, 73, 59.
HR EI MS: calculated for C24H33IOSi 492.1345; foun d 492.1327. [α ]2D2 –86 (c 0.27).
Triisopropyl((S)-3-{[1-({2-[4-(triisopropylsilyl)but-3-yn -1-yl]-1-n aph th yl}-eth yn yl)-
2-n aph th yl]m eth oxy}but-1-yn -1-yl)silan e (18)
A Sch len k flask was ch arged with [Pd(PPh 3)4] (56 m g, 0.050 m m ol, 5 m ole %), CuI (18 m g,
0.100 m m ol, 10 m ole %), an d flush ed with argon . Iodide (–)-(S)-17 (473 m g, 0.960 m m ol) in
diisopropylam in e (14 m l) was added an d th e m ixture was stirred at room tem perature for
10 m in . Th en diyn e 9 (380 m g, 1.05 m m ol, 1.10 equiv.) in diisopropylam in e (10 m l) was
added an d th e m ixture was stirred at room tem perature for 1 h . Volatiles were rem oved in
vacuo an d th e residue was ch rom atograph ed on silica gel (h exan es–eth er 99:1) to afford
(–)-(S)-18 (564 m g, 81%) as an oil. 1H NMR: 0.90–1.02 (42 H, m ); 1.55 (3 H, d, J = 6.6); 2.81
(2 H, t, J = 7.3); 3.42 (2 H, t, J = 7.3); 4.42 (1 H, q, J = 6.6); 5.18 (1 H, d, J = 12.4); 5.31 (1 H,
d, J = 12.4); 7.50 (1 H, ddd, J = 8.0, 6.8, 1.2); 7.53 (1 H, ddd, J = 8.1, 6.8, 1.2); 7.55 (1 H, d,
J = 8.4); 7.59 (1 H, ddd, J = 8.3, 6.8, 1.3); 7.62 (1 H, ddd, J = 8.4, 6.8, 1.4); 7.73 (1 H, d, J =
8.4); 7.80 (1 H, brd, J = 8.4); 7.86 (1 H, ddt, J = 8.0, 1.4, 0.7, 0.7); 7.88 (1 H, dt, J = 8.4, 0.8,
0.8); 7.88 (1 H, ddt, J = 8.1, 0.7, 0.7); 8.57 (1 H, ddt, J = 8.3, 1.2, 0.8, 0.8); 8.58 (1 H, ddt, J =
8.4, 1.2, 0.8, 0.8). 13C NMR: 11.08 (d), 11.27 (d), 18.47 (q), 18.56 (q), 21.39 (t), 22.51 (q),
34.90 (t), 65.69 (d), 69.33 (t), 81.42 (s), 86.08 (s), 94.23 (s), 95.84 (s), 107.56 (s), 107.88 (s),
119.28 (s), 119.48 (s), 125.74 (d), 125.78 (d), 126.21 (d), 126.24 (d), 126.34 (d), 126.90 (d),
127.08 (d), 127.68 (d), 128.11 (d), 128.21 (d), 128.44 (d), 128.59 (d), 132.08 (s), 132.67 (s),
133.44 (s), 133.78 (s), 139.01 (s), 141.69 (s). IR: 3059 w, 2891 m , 2866 vs, 2169 w, 1620 vw,
1593 w, 1570 w, 1508 w, 1463 m , 1399 w, 1383 w, 1372 w, 1367 w, 1251 w, 1096 m ,
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

Synthetic Studies Toward Chiral Aromatic Triynes
2205
996 m , 883 s, 867 w, 818 m , 678 s, 661 m , 617 w. EI MS: 725 (M• +, 2), 724 (3), 682 (0.8),
613 (1.6), 530 (1.2), 515 (32), 492 (18), 449 (78), 419 (12), 353 (14), 341 (10), 325 (12), 307
(10), 289 (6), 279 (72), 267 (100), 251 (9), 235 (10), 227 (20), 208 (10), 199 (24), 192 (44),
181 (16), 167 (24), 157 (16), 141 (67), 125 (36), 111 (38), 97 (37), 83 (50), 73 (62), 59 (58),
41 (54). HR EI MS: calculated for C36H39OSi (M• + – 210) 515.2770; foun d 515.2789.
[α ]2D2 –110 (c 1.21).
1-Iodo-2-{[((S)-1-m eth yl-3-p-tolylprop-2-yn -1-yl)oxy]m eth yl}n aph th alen e (19)
A Sch len k flask was ch arged with (–)-(S)-11 (623 m g, 3.89 m m ol, 1.50 equiv.) an d flush ed
with argon . Tetrah ydrofuran (10 m l) was added an d th e solution was cooled to –30 °C.
Dim eth yl sulfoxide (1.10 m l) was added followed by butyllith ium (1.6 M solution , 2.4 m l,
3.89 m m ol, 1.50 equiv.). Th e reaction m ixture was stirred at 0 °C for 10 m in . Brom ide 6
(900 m g, 2.59 m m ol) in tetrah ydrofuran (7 m l) was added an d th e reaction m ixture was
stirred at 40 °C for 16 h . Volatiles were rem oved in vacuo an d th e residue was
ch rom atograph ed on silica gel (h exan es–eth er 99:1 to 95:5) to afford (–)-(S)-19 (730 m g,
66%) as an oil. 1H NMR: 1.62 (3 H, d, J = 6.6); 2.35 (3 H, s); 4.57 (1 H, q, J = 6.6); 4.91 (1 H,
d, J = 12.8); 5.16 (1 H, d, J = 12.8); 7.11 (2 H, m ); 7.35 (2 H, m ); 7.50 (1 H, ddd, J = 8.0, 6.8,
1.2); 7.57 (1 H, ddd, J = 8.6, 6.8, 1.5); 7.64 (1 H, d, J = 8.4); 7.77 (1 H, brdd, J = 8.0, 1.5);
7.82 (1 H, brd, J = 8.4); 8.26 (1 H, ddt, J = 8.6, 1.2, 0.9, 0.9). 13C NMR: 21.46 (q), 22.26 (q),
65.79 (d), 76.04 (t), 85.70 (s), 88.14 (s), 103.57 (s), 119.65 (s), 126.40 (d), 126.46 (d), 127.67
(d), 128.27 (d), 128.73 (d), 129.02 (d), 131.67 (d), 132.36 (d), 133.72 (s), 134.72 (s), 138.45
(s), 139.91 (s). IR: 3058 w, 2226 w, 1620 vw, 1551 w, 1546 vw, 1510 m , 1502 w, 1425 w,
1374 w, 1327 m , 1095 vs, 1020 s, 863 m , 817 vs, 704 vw, 523 w. EI MS: 340 (6), 279 (2), 267
(18), 255 (100), 157 (7), 149 (18), 141 (39), 140 (26), 129 (42), 115 (15), 95 (10), 83 (15), 71
(23), 57 (43), 43 (34). FAB MS: 267, 255, 239, 215, 189, 165, 152, 143, 141, 115, 91, 77, 69, 55.
[α ]2D2 –112 (c 0.20).
Trimethyl[(2-{[((S)-1-methyl-3-p-tolylprop-2-yn-1-yl)oxy]methyl}-1-naphthyl)ethynyl]silane (20)
A pressure glass tube with a side arm an d a PTFE stopcock was ch arged with [Pd(PPh 3)4]
(12 m g, 0.011 m m ol, 5 m ole %), CuI (4 m g, 0.021 m m ol, 10 m ole %), iodide (–)-(S)-19
(90 m g, 0.210 m m ol), an d flush ed with argon . Degassed diisopropylam in e (2 m l) was added
followed by (trim eth ylsilyl)acetylen e (36 µl, 0.250 m m ol, 1.20 equiv.). Th e tube was tigh tly
closed an d th e reaction m ixture was stirred at 80 °C for 2 h . Volatiles were rem oved in
vacuo an d th e residue was ch rom atograph ed on silica gel (h exan es–eth er 99:1) to afford
(–)-(S)-20 (68 m g, 81%) as an oil. 1H NMR: 0.30 (9 H, s); 1.60 (3 H, d, J = 6.6); 2.34 (3 H,
brs); 4.56 (1 H, q, J = 6.6); 5.03 (1 H, d, J = 12.7); 5.15 (1 H, d, J = 12.7); 7.10 (2 H, m ); 7.33
(2 H, m ); 7.49 (1 H, ddd, J = 8.1, 6.8, 1.2); 7.56 (1 H, ddd, J = 8.4, 6.8, 1.4); 7.67 (1 H, d, J =
8.5); 7.82 (1 H, brd, J = 8.5); 7.82 (1 H, ddt, J = 8.1, 1.4, 0.7, 0.7); 8.35 (1 H, ddt, J = 8.4, 1.2,
0.8, 0.8). 13C NMR: 0.08 (q), 21.44 (q), 22.28 (q), 65.83 (d), 69.16 (t), 85.30 (s), 88.42 (s),
100.52 (s), 105.09 (s), 118.78 (s), 119.75 (s), 125.31 (d), 126.15 (d), 126.24 (d), 126.87 (d),
128.07 (d), 128.67 (d), 128.95 (d), 131.67 (d), 132.44 (s), 133.38 (s), 138.32 (s), 139.67 (s).
IR: 3060 w, 3009 s, 2900 m , 2226 w, 2148 m , 1621 vw, 1607 vw, 1593 w, 1568 w, 1510 s,
1408 w, 1374 m , 1328 s, 1260 m , 1251 s, 1181 w, 1130 m (sh ), 1095 s, 1027 m (sh ),
1021 m , 872 vs, 846 vs, 820 vs, 701 w, 644 m , 570 w, 525 w, 405 w. EI MS: 396 (M• +, 2),
381 (5), 323 (10), 310 (3), 279 (2), 265 (34), 253 (4), 237 (8), 178 (6), 165 (9), 143 (16), 129
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

2206
Alexandrová et al.:
(31), 115 (6), 73 (100), 59 (14). HR EI MS: calculated for C27H28OSi 396.1909; foun d
396.1922. [α ]2D2 –128 (c 0.14).
1-Eth yn yl-2-{[((S)-1-m eth yl-3-p-tolylprop-2-yn -1-yl)oxy]m eth yl}n aph th alen e (21)
Sodium m eth oxide (3.3 M solution in m eth an ol, 70 µl, 0.230 m m ol, 1.70 equiv.) was added
to (–)-(S)-20 (53 m g, 0.130 m m ol) in tetrah ydrofuran (2 m l) un der argon . Th e reaction m ix-
ture was stirred at room tem perature for 1 h . Th e solven t was evaporated in vacuo an d th e
residue was ch rom atograph ed on silica gel (h exan es–eth er 99:1) to afford (–)-(S)-21 (35 m g,
81%) as an oil. 1H NMR: 1.59 (3 H, d, J = 6.6); 2.35 (3 H, brs); 3.70 (1 H, s); 4.54 (1 H, q, J =
6.6); 5.07 (1 H, d, J = 12.5); 5.18 (1 H, d, J = 12.5); 7.11 (2 H, m ); 7.34 (2 H, m ); 7.51 (1 H,
ddd, J = 8.1, 6.8, 1.3); 7.57 (1 H, ddd, J = 8.4, 6.8, 1.4); 7.69 (1 H, d, J = 8.5); 7.76 (1 H, brd,
J = 8.5); 7.84 (1 H, ddt, J = 8.1, 1.4, 0.7, 0.7); 8.38 (1 H, ddt, J = 8.4, 1.3, 0.8, 0.8). 13C NMR:
21.45 (q), 22.26 (q), 65.65 (d), 68.99 (t), 79.27 (s), 85.41 (s), 87.18 (d), 88.43 (s), 117.93 (s),
119.78 (s), 125.53 (d), 126.13 (d), 126.28 (d), 127.00 (d), 128.12 (d), 128.99 (2 × d),
131.64 (d), 132.47 (s), 133.58 (s), 138.37 (s), 139.98 (s). IR: 3304 s, 3061 w, 3033 w, 2226 w,
2100 vw, 1621 vw, 1608 vw, 1594 w, 1569 w, 1510 s, 1431 w (sh ), 1407 vw (sh ), 1373 m ,
1328 s, 1259 w, 1175 w, 1106 s (sh ), 1095 vs, 1022 m , 869 w, 835 w, 820 vs, 658 m , 617 m ,
438 w. EI MS: 324 (M• +, 4), 323 (13), 309 (26), 281 (23), 265 (15), 193 (100), 165 (61), 152
(24), 143 (28), 129 (53), 115 (22), 91 (7), 63 (6), 51 (5), 43 (17). HR EI MS: calculated for
C
24H20O 324.1514; foun d 324.1504. [α ]2D2 –169 (c 0.09).
Triisopropyl(4-{1-[(2-{[((S)-1-m eth yl-3-p-tolylprop-2-yn -1-yl)oxy]m eth yl}-1-n aph th yl)-
eth yn yl]-2-n aph th yl}but-1-yn -1-yl)silan e (22)
A Sch len k flask was ch arged with [Pd(PPh 3)4] (5 m g, 0.005 m m ol, 5 m ole %), CuI (2 m g,
0.009 m m ol, 10 m ole %), iodide 8 (45 m g, 0.095 m m ol, 1.10 equiv.), an d flush ed with
argon . Degassed diisopropylam in e (1 m l) was added followed by diyn e (–)-(S)-21 (28 m g,
0.086 m m ol) in diisopropylam in e (1 m l). Th e reaction m ixture was stirred at room tem pera-
ture for 1 h . Volatiles were rem oved in vacuo an d th e residue was ch rom atograph ed on
silica gel (h exan es–eth er 98:2) to afford (–)-(S)-22 (33 m g, 58%) as an oil. 1H NMR: 0.86–1.02
(21 H, m ); 1.62 (3 H, d, J = 6.6); 2.28 (3 H, s); 2.89 (2 H, t, J = 5.7); 3.92 (2 H, t, J = 5.7);
4.60 (1 H, d, J = 6.6); 5.26 (1 H, d, J = 12.6); 5.37 (1 H, d, J = 12.6); 6.91 (2 H, m ); 7.15 (2 H,
m ); 7.47 (1 H, ddd, J = 8.0, 6.9, 1.3); 7.52 (1 H, d, J = 8.4); 7.54 (1 H, ddd, J = 8.1, 6.8, 1.2);
7.54 (1 H, ddd, J = 8.4, 6.9, 1.4); 7.63 (1 H, ddd, J = 8.4, 6.8, 1.4); 7.77 (1 H, d, J = 8.5); 7.78
(1 H, brd, J = 8.4); 7.84 (1 H, ddt, J = 8.0, 1.4, 0.8, 0.8); 7.89 (1 H, ddt, J = 8.1, 1.4, 0.8, 0.8);
7.90 (1 H, brd, J = 8.5); 8.59 (1 H, ddt, J = 8.4, 1.2, 0.8, 0.8); 8.60 (1 H, ddt, J = 8.4, 1.3, 0.8,
0.8). 13C NMR: 11.28 (d), 18.56 (q), 21.34 (t), 21.39 (q), 22.36 (q), 34.83 (t), 65.64 (d), 69.39
(t), 81.39 (s), 85.62 (s), 88.29 (s), 94.28 (s), 95.98 (s), 107.90 (s), 119.32 (s), 119.46 (s),
119.51 (s), 125.65 (d), 125.78 (d), 126.24 (d), 126.27 (d), 126.30 (d), 126.96 (d), 127.11 (d),
127.67 (d), 128.06 (d), 128.24 (d), 128.39 (d), 128.66 (d), 128.79 (d), 131.53 (d), 132.08 (s),
132.70 (s), 133.44 (s), 133.74 (s), 138.13 (s), 138.98 (s), 141.75 (s). IR: 3059 w, 3008 m ,
2864 vs, 2226 w, 2170 m , 1620 vw, 1608 vw, 1593 w, 1570 w, 1510 s, 1463 s, 1399 m ,
1380 m , 1368 w (sh ), 1375 m (sh ), 1327 m , 1265 m , 1129 w (sh ), 1105 m (sh ), 1094 s,
1075 m , 1021 m , 997 m , 884 m , 867 w, 819 s, 679 m , 660 m , 616 w, 524 w, 427 w. EI MS:
658 (M• +, 2), 615 (3), 515 (8), 449 (6), 341 (16), 326 (8), 302 (10), 289 (11), 187 (6), 173
(15), 159 (23), 143 (100), 129 (23), 115 (36), 103 (10), 87 (26), 73 (48), 59 (52), 43 (35).
HR EI MS: calculated for C47H50OSi 658.3631; foun d 658.3661. [α ]2D2 –59 (c 0.10).
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

Synthetic Studies Toward Chiral Aromatic Triynes
2207
1-Brom o-2-(but-3-yn -1-yl)n aph th alen e (23)
Tetrabutylam m on ium fluoride (1
M solution in tetrah ydrofuran , 371 µl, 0.400 m m ol,
1.10 equiv.) was added to silylated alkyn e 7 (150 m g, 0.360 m m ol) in tetrah ydrofuran (5 m l)
un der argon . Th e m ixture was stirred at room tem perature for 20 m in . Th e solven t was
evaporated in vacuo an d th e residue was ch rom atograph ed on silica gel (petroleum eth er–
eth er 99:1) to afford un protected alkyn e 23 (93 m g, 99%) as an oil. 1H NMR: 1.99 (1 H, t,
J = 2.6); 2.61 (2 H, dt, J = 7.6, 7.6, 2.6); 3.23 (2 H, t, J = 7.6); 7.41 (1 H, d, J = 8.4); 7.49 (1 H,
ddd, J = 8.1, 6.9, 1.2); 7.58 (1 H, ddd, J = 8.6, 6.9, 1.4); 7.76 (1 H, brd, J = 8.4); 7.81 (1 H,
ddt, J = 8.1, 1.4, 0.7, 0.7); 8.32 (1 H, ddt, J = 8.6, 1.0, 0.9, 0.9). 13C NMR: 18.93 (t), 36.38 (t),
69.19 (d), 83.38 (s), 123.89 (s), 126.10 (d), 127.27 (d), 127.38 (d), 127.55 (d), 128.04 (d),
128.20 (d), 132.54 (s), 133.46 (s), 137.74 (s). IR: 3308 vs, 3058 w, 3013 m , 2944 w, 2918 w,
2871 w, 2842 w, 2119 w, 1624 w, 1598 w, 1558 w, 1502 m , 1463 w, 1453 w, 1431 w,
1353 m , 1329 m , 1259 m , 1253 m , 1146 w, 1135 w, 1031 w, 1016 w, 969 m , 928 w, 905 w,
864 w, 816 s, 643 vs, 639 vs (sh ), 480 vw, 470 w, 411 w. EI MS: 260 (M• + with 81Br, 30), 258
(M• + with 79Br, 30), 221 (97), 219 (100), 179 (67), 152 (7), 140 (50), 89 (8), 76 (8), 63 (9).
FAB MS: 259, 232, 221, 215, 197, 186, 181, 165, 152, 141, 123, 115, 110, 105, 91, 75.
HR EI MS: calculated for C14H1181Br 260.0024 an d for C14H1179Br 258.0044; foun d 260.0014
an d 258.0043, respectively.
1-Brom o-2-(4-p-tolylbut-3-yn -1-yl)n aph th alen e (24)
A Sch len k flask was ch arged with [Pd(PPh 3)4] (18 m g, 0.016 m m ol, 5 m ole %), CuI (6 m g,
0.031 m m ol, 10 m ole %), 4-iodotoluen e (67 m g, 0.310 m m ol, 1.00 equiv.), an d flush ed with
argon . Alkyn e 23 (80 m g, 0.310 m m ol) in diisopropylam in e (3 m l) was added an d th e m ix-
ture was stirred at room tem perature for 2 h . Volatiles were rem oved in vacuo an d th e resi-
due was ch rom atograph ed on silica gel (h exan es–eth er 98:2) to afford 24 (105 m g, 97%) as
an oil. 1H NMR: 2.32 (3 H, s); 2.81 (2 H, t, J = 7.5); 3.30 (2 H, t, J = 7.5); 7.06–7.09 (2 H, m );
7.24–7.27 (2 H, m ); 7.46 (1 H, d, J = 8.3); 7.49 (1 H, ddd, J = 8.1, 6.8, 1.2); 7.58 (1 H, ddd,
J = 8.5, 6.8, 1.3); 7.76 (1 H, brd, J = 8.3); 7.81 (1 H, ddt, J = 8.1, 1.3, 0.7, 0.7); 8.33 (1 H, ddt,
J = 8.5, 1.0, 0.8, 0.8). 13C NMR: 20.00 (t), 21.39 (q), 36.71 (t), 81.61 (s), 88.24 (s), 120.68 (s),
123.92 (s), 126.03 (d), 127.31 (d), 127.33 (d), 127.45 (d), 128.03 (d), 128.41 (d), 128.95 (d),
131.40 (d), 132.57 (s), 133.46 (s), 137.64 (s), 138.11 (s). IR: 3075 m (sh ), 3056 s, 3035 m ,
3011 vs, 2235 vw, 2225 vw, 1623 w, 1609 w, 1599 m , 1558 s, 1510 vs, 1502 vs, 1463 m ,
1452 s, 1430 s, 1407 w, 1375 m , 1354 s, 1344 s, 1331 s, 1308 w (sh ), 1273 m , 1258 s,
1181 w, 1146 w, 1135 w, 1119 w, 1043 w (sh ), 1031 m , 1022 m , 1013 m , 969 s, 946 w,
932 m , 907 m , 863 m , 818 vs, 642 m , 531 vs, 477 w, 469 w, 413 m . EI MS: 350 (M• + with
81Br, 0.95), 348 (M• + with 79Br, 1), 269 (100), 254 (14), 221 (23), 219 (24), 140 (28), 129
(33), 85 (9), 77 (6), 71 (12), 57 (22), 43 (20). FAB MS: 349, 307, 289, 279, 271, 257, 232, 215,
197, 181, 165, 147, 141, 131, 123, 110, 91, 75, 57. HR EI MS: calculated for C21H1781Br
350.0493 an d C21H1779Br 348.0513; foun d 350.0507 an d 348.0511, respectively.
1-Iodo-2-(4-p-tolylbut-3-yn -1-yl)n aph th alen e (25)
Butyllith ium (1.6 M solution , 147 µl, 0.240 m m ol, 1.04 equiv.) was added to 24 (80 m g,
0.230 m m ol) in tetrah ydrofuran (2 m l) at –78 °C un der argon . Th e m ixture was stirred
15 m in at –78 °C. Iodin e (63 m g, 0.250 m m ol, 1.10 equiv.) in tetrah ydrofuran (1.5 m l) was
added an d th e reaction m ixture was stirred at –78 °C for 1 h . Th e solven t was evaporated in
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

2208
Alexandrová et al.:
vacuo an d th e residue was partition ed between eth er an d water. Th e organ ic layer was sepa-
rated, wash ed with aqueous Na2S2O3 (2×), water, an d dried over an h ydrous Na2SO4.
Volatiles were rem oved in vacuo an d th e residue was ch rom atograph ed on silica gel (petro-
leum eth er–eth er 98:2) to afford iodide 25 (83 m g, 93%) as an oil. 1H NMR: 2.33 (3 H, s);
2.80 (2 H, t, J = 7.5); 3.34 (2 H, t, J = 7.5); 7.08 (2 H, m ); 7.27 (2 H, m ); 7.47 (1 H, d, J = 8.5);
7.48 (1 H, ddd, J = 8.1, 6.8, 1.2); 7.56 (1 H, ddd, J = 8.5, 6.8, 1.4); 7.76 (1 H, brd, J = 8.5);
7.76 (1 H, ddt, J = 8.1, 1.4, 0.7, 0.7); 8.26 (1 H, ddt, J = 8.5, 1.2, 0.8, 0.8). 13C NMR: 20.31
(t), 21.40 (q), 41.98 (t), 81.69 (s), 88.08 (s), 105.39 (s), 120.67 (s), 126.06 (d), 127.70 (d),
127.82 (d), 128.16 (d), 128.56 (d), 128.95 (d), 131.42 (d), 132.76 (d), 132.95 (s), 135.13 (s),
137.65 (s), 142.59 (s). IR: 3081 w (sh ), 3055 m , 3033 w, 3011 s, 2233 vw, 1621 w, 1599 w,
1551 m , 1510 vs, 1501 s, 1452 m , 1429 m , 1407 w, 1379 w, 1351 w, 1342 w, 1326 m , 1271 w,
1257 m , 1180 w, 1145 w, 1132 w, 1119 w, 1042 w (sh ), 1032 w, 1022 w, 1011 w, 960 m ,
947 w (sh ), 928 w, 901 w, 862 w, 819 vs, 636 w, 524 m , 478 w, 465 vw, 410 w. EI MS: 396
(M• +, 12), 269 (67), 255 (16), 239 (6), 141 (100), 129 (28), 115 (16), 71 (6), 57 (10), 43 (7).
FAB MS: 397, 377, 307, 289, 271, 257, 232, 215, 197, 181, 165, 149, 142, 131, 123, 110, 91,
75. HR EI MS: calculated for C21H17I 396.0375; foun d 396.0370.
2-Meth yl-4-{2-[4-(triisopropylsilyl)but-3-yn -1-yl]-1-n aph th yl}but-3-yn -2-ol (26)
A Sch len k flask was ch arged with [Pd(PPh 3)4] (63 m g, 0.050 m m ol, 5 m ole %), CuI (21 m g,
0.110 m m ol, 10 m ole %), iodide
8 (500 m g, 1.08 m m ol), an d flush ed with argon .
Diisopropylam in e (8 m l) was added followed by alkyn e 13 (380 µl, 3.89 m m ol, 3.60 equiv.).
Th e m ixture was stirred at 80 °C for 2 h . Volatiles were rem oved in vacuo an d th e residue
was ch rom atograph ed on silica gel (h exan es–eth er–aceton e 98:2:0 to 80:10:10) to afford 26
(390 m g, 86%) as an oil. 1H NMR: 0.98–1.06 (21 H, m ); 1.75 (6 H, s); 2.67 (2 H, t, J = 7.5);
3.21 (2 H, t, J = 7.5); 7.41 (1 H, d, J = 8.4); 7.46 (1 H, ddd, J = 8.1, 6.8, 1.2); 7.54 (1 H, ddd,
J = 8.4, 6.8, 1.4); 7.74 (1 H, brd, J = 8.4); 7.80 (1 H, ddt, J = 8.1, 1.4, 0.7, 0.7); 8.28 (1 H, ddt,
J = 8.4, 1.2, 0.8, 0.8). 13C NMR: 11.27 (d), 18.59 (q), 20.95 (t), 31.69 (q), 34.95 (t), 66.04 (s),
78.56 (s), 81.01 (s), 103.46 (s), 108.08 (s), 118.67 (s), 125.73 (d), 125.91 (d), 126.76 (d),
127.28 (d), 128.02 (d), 128.31 (d), 131.92 (s), 133.47 (s), 141.75 (s). IR: 3599 m , 3059 w,
2865 vs, 2217 vw, 2170 m , 1621 w, 1595 w (sh ), 1567 w, 1508 w, 1463 s, 1429 w, 1383 s,
1365 m , 1328 m , 1273 w, 1115 m , 1026 w, 996 m , 886 w, 884 s, 821 m , 679 m , 660 s, 627 m .
EI MS: 418 (M• +, 12), 375 (46), 333 (14), 317 (13), 303 (7), 287 (8), 273 (16), 261 (27), 245
(32), 229 (30), 215 (16), 202 (23), 191 (30), 178 (18), 165 (41), 152 (16), 131 (25), 115 (11),
103 (70), 75 (100), 61 (66), 43 (48). HR EI MS: calculated for C28H38OSi 418.2691; foun d
418.2675.
4-[2-(But-3-yn -1-yl)-1-n aph th yl]-2-m eth ylbut-3-yn -2-ol (27)
Tetrabutylam m on ium fluoride (1
M solution in tetrah ydrofuran , 450 µl, 0.480 m m ol,
3.30 equiv.) was added to silylated diyn e 26 (61 m g, 0.150 m m ol) in tetrah ydrofuran
(2.5 m l) un der argon . Th e m ixture was stirred at room tem perature for 45 m in . Th e solven t
was evaporated in vacuo an d th e residue was ch rom atograph ed on silica gel (petroleum
eth er–eth er–aceton e 80:10:10) to afford diyn e 27 (28 m g, 74%) as an oil. 1H NMR: 1.75 (6 H,
s); 1.99 (1 H, t, J = 2.7); 2.61 (2 H, dt, J = 7.5, 7.5, 2.7); 3.21 (2 H, t, J = 7.5); 7.39 (1 H, d, J =
8.5); 7.47 (1 H, ddd, J = 8.1, 6.8, 1.3); 7.55 (1 H, ddd, J = 8.4, 6.8, 1.4); 7.76 (1 H, brd, J =
8.5); 7.81 (1 H, ddt, J = 8.1, 1.4, 0.6, 0.6); 8.28 (1 H, ddt, J = 8.4, 1.3, 0.8, 0.8). 13C NMR:
19.54 (t), 31.69 (q), 34.47 (t), 66.04 (s), 68.95 (d), 78.49 (s), 83.81 (s), 103.55 (s), 118.81 (s),
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

Synthetic Studies Toward Chiral Aromatic Triynes
2209
125.86 (d), 125.94 (d), 126.88 (d), 127.17 (d), 128.07 (d), 128.41 (d), 131.94 (s), 133.48 (s),
141.42 (s). IR: 3598 w, 3308 m , 3059 w, 2218 vw, 2118 vw, 1621 vw, 1593 w, 1567 vw,
1508 w, 1463 w, 1455 w, 1431 w, 1383 m , 1365 m , 1329 m , 1273 w, 1115 w, 1026 vw,
868 w, 820 m , 650 m . EI MS: 262 (M• +, 19), 247 (22), 229 (12), 219 (15), 209 (7), 202 (22),
189 (21), 178 (25), 165 (50), 152 (9), 141 (50), 115 (7), 83 (6), 69 (9), 57 (17), 43 (100).
HR EI MS: calculated for C19H18O 262.1357; foun d 262.1348.
2-Meth yl-4-[2-(4-p-tolylbut-3-yn -1-yl)-1-n aph th yl]but-3-yn -2-ol (28)
A Sch len k flask was ch arged with [Pd(PPh 3)4] (9 m g, 0.008 m m ol, 5 m ole %), CuI (3 m g,
0.016 m m ol, 10 m ole %), 4-iodotoluen e (37 m g, 0.170 m m ol, 1.10 equiv.), an d flush ed with
argon . Alkyn e 27 (40 m g, 0.150 m m ol) in diisopropylam in e (1.5 m l) was added an d th e
m ixture was stirred at room tem perature for 30 m in . Volatiles were rem oved in vacuo an d
th e residue was ch rom atograph ed on silica gel (petroleum eth er–eth er–aceton e 80:10:10) to
afford 28 (42 m g, 78%) as an oil. 1H NMR: 1.74 (6 H, s) 2.32 (3 H, s); 2.81 (2 H, t, J = 7.5);
3.27 (2 H, t, J = 7.5); 7.07 (2 H, m ); 7.25 (2 H, m ); 7.44 (1 H, d, J = 8.4); 7.47 (1 H, ddd, J =
8.1, 6.8, 1.2); 7.56 (1 H, ddd, J = 8.4, 6.8, 1.3); 7.77 (1 H, brd, J = 8.4); 7.81 (1 H, ddt, J =
8.1, 1.4, 0.6, 0.6); 8.30 (1 H, ddt, J = 8.4, 1.2, 0.8, 0.8). 13C NMR: 20.64 (t), 21.38 (q), 31.67
(q), 34.76 (t), 66.03 (s), 78.63 (s), 81.46 (s), 88.63 (s), 103.39 (s), 118.86 (s), 120.74 (s),
125.78 (d), 125.95 (d), 126.82 (d), 127.36 (d), 128.06 (d), 128.31 (d), 128.94 (d), 131.39 (d),
131.93 (s), 133.51 (s), 137.61 (s), 141.77 (s). IR: 3598 m , 3080 w, 3059 w, 2219 vw, 1621 vw,
1593 w, 1567 w, 1510 vs, 1451 w, 1435 w, 1408 w (sh ), 1383 m , 1365 m , 1329 m , 1274 w,
1179 m , 1162 m , 1146 m , 1116 m , 1041 vw, 1022 w, 956 m , 868 w, 846 w, 819 vs, 531 m .
EI MS: 352 (M• +, 1), 337 (100), 276 (7), 262 (8), 211 (8), 205 (12), 179 (14), 165 (40), 149
(7), 141 (14), 128 (10), 119 (17), 97 (11), 83 (14), 69 (19), 57 (30), 43. FAB MS: 353, 335,
319, 305, 289, 279, 265, 239, 226, 215, 202, 193, 186, 179, 165, 152, 141,129, 115, 105, 93,
73. HR EI MS: calculated for C26H24O (M• + – CH3) 337.1592; foun d 337.1588.
1-Eth yn yl-2-(4-p-tolylbut-3-yn -1-yl)n aph th alen e (29)
Sodium h ydride (80% suspen sion in m in eral oil, 30 m g, 1.17 m m ol, 2.50 equiv.) was added
to diyn e 28 (138 m g, 0.390 m m ol) in toluen e (6 m l) un der argon . Th e m ixture was stirred at
110 °C for 40 m in , th en cooled to room tem perature, an d partition ed between eth er an d wa-
ter. Th e organ ic layer was separated, wash ed with brin e (2×), an d dried over an h ydrous
Na2SO4. Volatiles were rem oved in vacuo an d th e residue was ch rom atograph ed on silica gel
(petroleum eth er–eth er–aceton e 80:10:10) to afford 29 (90 m g, 78%) as an oil. 1H NMR: 2.33
(3 H, s); 2.82 (2 H, t, J = 7.5); 3.32 (2 H, t, J = 7.5); 3.72 (1 H, s); 7.09 (2 H, m ); 7.26 (2 H,
m ); 7.47 (1 H, d, J = 8.4); 7.48 (1 H, ddd, J = 8.1, 6.8, 1.2); 7.57 (1 H, ddd, J = 8.4, 6.8, 1.4);
7.80 (1 H, brd, J = 8.4); 7.82 (1 H, ddt, J = 8.1, 1.4, 0.8, 0.8); 8.38 (1 H, ddt, J = 8.4, 1.2, 0.9,
0.9). 13C NMR: 20.66 (t), 21.40 (q), 34.55 (t), 79.98 (s), 81.46 (s), 86.41 (d), 88.62 (s),
118.28 (s), 120.78 (s), 125.87 (d), 126.03 (d), 126.98 (d), 127.36 (d), 128.09 (d), 128.73 (d),
128.94 (d), 131.41 (d), 131.86 (s), 133.90 (s), 137.58 (s), 141.64 (s). IR: 3304 s, 3081 w,
3059 w, 2228 vw, 2098 w, 1621 w, 1602 w, 1593 w, 1568 w, 1510 vs, 1451 w, 1431 w,
1407 vw, 1374 w, 1343 w, 1328 w, 1275 vw, 1268 w, 1181 w, 1146 w, 1118 w, 1041 vw,
1022 w, 868 w, 819 vs, 654 m , 613 m , 557 w, 529 m . EI MS: 294 (M• +, 61), 279 (40), 202
(9), 189 (8), 165 (100), 139 (14), 129 (26), 115 (9), 77 (6), 69 (9), 57 (11), 43 (10). FAB MS:
295, 279, 257, 232, 215, 197, 186, 181, 165, 149, 131, 119, 110, 91, 75. HR EI MS: calculated
for C23H18 294.1408; foun d 294.1402.
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

2210
Alexandrová et al.:
Triisopropyl{(S)-3-[(1-{[2-(4-p-tolylbut-3-yn -1-yl)-1-n aph th yl]eth yn yl}-2-n aph th yl)m eth oxy]-
but-1-yn -1-yl}silan e (30)
A Sch len k flask was ch arged with [Pd(PPh 3)4] (9 m g, 0.010 m m ol, 5 m ole %), CuI (3.5 m g,
0.020 m m ol, 10 m ole %), iodide (–)-(S)-17 (85 m g, 0.170 m m ol, 1.01 equiv.), an d flush ed
with argon . Degassed diisopropylam in e (2 m l) was added followed by diyn e 29 (50 m g,
0.170 m m ol) in diisopropylam in e (2 m l). Th e reaction m ixture was stirred at room tem pera-
ture for 1 h an d th en at 80 °C for 2 h . Volatiles were rem oved in vacuo an d th e residue was
ch rom atograph ed on silica gel (h exan es–eth er 99:1) to afford (–)-(S)-30 (85 m g, 76%) as an
oil. 1H NMR: 0.90–1.00 (21 H, m ); 1.54 (3 H, d, J = 6.6); 2.32 (3 H, s); 2.94 (2 H, t, J = 7.5);
3.50 (2 H, t, J = 7.5); 4.43 (1 H, q, J = 6.6); 5.21 (1 H, d, J = 12.4); 5.31 (1 H, d, J = 12.4);
7.05 (2 H, m ); 7.24 (2 H, m ); 7.52 (2 H, ddd, J = 8.1, 6.8, 1.2); 7.55 (1 H, d, J = 8.4); 7.59
(1 H, ddd, J = 8.4, 6.8, 1.4); 7.61 (1 H, ddd, J = 8.4, 6.8, 1.4); 7.74 (1 H, d, J = 8.5); 7.84 (1 H,
brd, J = 8.4); 7.87 (1 H, brdd, J = 8.1, 1.4); 7.88 (1 H, brd, J = 8.5); 7.88 (1 H, brdd, J = 8.1,
1.4); 8.61 (2 H, brd, J = 8.4). 13C NMR: 11.09 (d), 18.49 (q), 21.12 (t), 21.38 (q), 22.49 (q),
35.07 (t), 65.75 (d), 69.37 (t), 81.64 (s), 86.08 (s), 88.58 (s), 94.26 (s), 95.86 (s), 107.61 (s),
119.22 (s), 119.64 (s), 120.78 (s), 125.72 (d), 125.86 (d), 126.24 (d), 126.33 (d), 126.38 (d),
127.00 (d), 127.12 (d), 127.52 (d), 128.15 (d), 128.20 (d), 128.55 (d), 128.62 (d), 128.89 (d),
131.43 (d), 132.09 (s), 132.68 (s), 133.47 (s), 133.82 (s), 137.52 (s), 139.13 (s), 141.70 (s). IR:
3083 w (sh ), 3060 w, 3011 s, 2866 vs, 2230 vvw, 2200 vvw (sh ), 2165 w, 1621 w, 1593 w,
1571 w, 1510 s, 1463 s, 1452 w, 1431 w, 1400 m , 1383 w, 1373 w, 1325 m , 1310 w (sh ),
1275 w, 1181 w, 1096 s, 1071 m , 1043 w, 1021 m , 997 m , 884 s, 867 w, 819 vs, 680 s,
663 m , 628 w (sh ), 530 w, 428 w. EI MS: 658 (M• +, 0.3), 505 (0.7), 485 (0.3), 471 (0.2), 449
(100), 421 (31), 329 (7), 302 (9), 289 (11), 255 (9), 141 (14), 129 (8), 105 (9), 73 (13), 59
(15), 43 (12). HR EI MS: calculated for C34H25OSi (M• + – 209) 449.1905; foun d 449.1912.
[α ]2D2 –58 (c 0.11).
The financial support by the Grant Agency of the Czech Republic (Grant No. 203/02/0248) and
by the Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic
(Project Z4 055 905) is gratefully acknowledged. We thank Dr J. Cvačka and the group of Dr K. Ubik
(IOCB) for the mass spectra.
REFERENCES AND NOTES
1. For reviews, see: a) Urbano A.: Angew. Chem., Int. Ed. 2003, 42, 3986; b) Hopf H.: Classics
in Hydrocarbon Chemistry: Syntheses, Concepts, Perspectives, Chap. 12.2, p. 323. VCH,
Weinheim 2000; c) Katz T. J.: Angew. Chem., Int. Ed. 2000, 39, 1921; d) Osuga H.,
Suzuki H.: J. Synth. Org. Chem., Jpn. 1994, 52, 1020; e) Oremek G., Seiffert U., Janecka A.:
Chem.-Ztg. 1987, 111, 69; f) Vögtle F.: Fascinating Molecules in Organic Chemistry, p. 156.
Wiley, New York 1992; g) Meurer K. P., Vögtle F.: Top. Curr. Chem. 1985, 127, 1;
h) Laarhoven W. H., Prinsen W. J. C.: Top. Curr. Chem. 1984, 125, 63; i) Martin R. H.:
Angew. Chem. 1974, 86, 727; j) Wynberg H.: Acc. Chem. Res. 1971, 4, 65.
2. Vanest J., Martin R. H.: Rec. Trav. Chim. Pays-Bas 1979, 98, 113.
3. Katz T. J., Sudhakar A., Teasley M. F., Gilbert A. M., Geiger W. E., Robben M. P.,
Wuensch M., Ward M. D.: J. Am. Chem. Soc. 1993, 115, 3182.
Collect. Czech. Chem. Commun. (Vol. 69) (2004)

Synthetic Studies Toward Chiral Aromatic Triynes
2211
4. a) Tanaka K., Osuga H., Suzuki H., Shogase Y., Kitahara Y.: J. Chem. Soc., Perkin Trans. 1
1998, 935; b) Tanaka K., Suzuki H., Osuga H.: J. Org. Chem. 1997, 62, 4465.
5. a) Carreñ o M. C., Garcia-Cerrada S., Urbano A.: Chem. Eur. J. 2003, 9, 4118; b) Carreñ o
M. C., Garcia-Cerrada S., Urbano A.: J. Am. Chem. Soc. 2001, 123, 7929.
6. For other recent examples of stoichiometric asymmetric synthesis of helicenes, see:
a) Nakano D., Hirano R., Yamaguchi M., Kabuto C.: Tetrahedron Lett. 2003, 44, 3683;
b) Ogawa Y., Toyama M., Karikomi M., Seki K., Haga K., Uyehara T.: Tetrahedron Lett.
2003, 44, 2167.
7. a) Teplý F., Stará I. G., Starý I., Kollárovič A., Šaman D., Vyskočil Š., Fiedler P.: J. Org.
Chem. 2003, 68, 5193; b) Stará I. G., Starý I., Kollárovič A., Teplý F., Vyskočil Š.,
Šaman D.: Tetrahedron Lett. 1999, 40, 1993.
8. In addition, Kagan, Martin, Buchardt, and Calvin described the absolute asymmetric
synthesis of helicenes under the influence of circularly polarized light but this approach
relates to the question of chirality origin on earth rather than to practical asymmetric
synthesis. For references, see: a) Moradpour A., Kagan H., Baes M., Morren G., Martin
R. H.: Tetrahedron 1975, 31, 2139; b) Buchardt O.: Angew. Chem. 1974, 86, 222;
c) Bernstein W. J., Calvin M., Buchardt O.: J. Am. Chem. Soc. 1973, 95, 527; d) Bernstein
W. J., Calvin M., Buchardt O.: J. Am. Chem. Soc. 1972, 94, 494; e) Bernstein W. J.,
Calvin M., Buchardt O.: Tetrahedron Lett. 1972, 2195; f) Kagan H., Moradpour A., Nicoud
J. F., Balavoine G., Martin R. H., Cosyn J. P.: Tetrahedron Lett. 1971, 2479; g) Moradpour A.,
Nicoud J. F., Balavoine G., Kagan H.: J. Am. Chem. Soc. 1971, 93, 2353.
9. For recent examples, see: a) Reetz M. T., Sostmann S.: Tetrahedron 2001, 57, 2515;
b) Thongpanchang T., Paruch K., Katz T. J., Rheingold A. L., Lam K. C., Liablesands L.:
J. Org. Chem. 2000, 65, 1850.
10. For recent examples of [2+2+2] cycloisomerization of triynes used in the synthesis of
helicenes or helicene-like molecules, see lit.7 and the following referencess: a) Stará I. G.,
Starý I., Kollárovič A., Teplý F., Šaman D., Fiedler P.: Collect. Czech. Chem. Commun.
2003, 68, 917; b) Teplý F., Stará I. G., Starý I., Kollárovič A., Šaman D., Rulíšek L.,
Fiedler P.: J. Am. Chem. Soc. 2002, 124, 9175; c) Stará I. G., Starý I., Kollárovič A., Teplý F.,
Šaman D., Tichý M.: J. Org. Chem. 1998, 63, 4046.
11. Stará I. G., Alexandrová Z., Teplý F., Sehnal P., Starý I., Šaman D., Buděšínský M.:
Unpublished results.
12. Stará I. G., Kollárovič A., Teplý F., Starý I., Šaman D., Fiedler P.: Collect. Czech. Chem.
Commun. 2000, 65, 577.
13. Nakamura K., Takenaka K., Ohno A.: Tetrahedron: Asymmetry 1998, 9, 4429.
14. Holander G. A., Harring L. S.: J. Org. Chem. 1990, 55, 6171.
Collect. Czech. Chem. Commun. (Vol. 69) (2004)