Synthesis of 2-hydroxy-8′-(hydroxymethyl)-1,1′-binaphthalene (iso-homo-binol). A new structural pattern in the binaphthyl realm

Article abstract of DOI:10.1135/cccc20030907

The title compound 7 has been synthesized in a racemic form, using Suzuki coupling (8 + 15 → 16) as the key step. Pure enantiomer (S)-(-)-7 has been obtained by carbonylation of the known bromide (S)-(+)-12 followed by reduction of the resulting methyl ester (S)-(+)-18 with LiAlH₄.

Full text of DOI:10.1135/cccc20030907

Synthesis of 2-Hydroxy-8′-(hydroxymethyl)-1,1′-binaphthalene
907
SYNTHESIS OF 2-HYDROXY-8′-(HYDROXYMETHYL)-
1,1′-BINAPHTHALENE (iso-HOMO-BINOL).
A NEW STRUCTURAL PATTERN IN THE BINAPHTHYL REALM
a
c
Štěpán VYSKOČILa,b,*, Stephen C. LOCKHART , William L. MITCHELL and
a1,
Pavel KOČOVSKÝ
*
a
Department of Chemistry, University of Glasgow, Glasgow G12 8QQ, U.K.;
1
e-mail: p.kocovsky@chem.gla.ac.uk
b
c
Department of Organic Chemistry, Charles University, 128 40 Prague 2, Czech Republic;
e-mail: stepanv@natur.cuni.cz
Department of Chemistry, GlaxoSmithKline PLC, The Frythe, Welwyn, Herts. AL6 9AR, U.K.
Received Jan uary 2, 2003
Accepted Jan uary 28, 2003
Dedicated to the memory of Professor Otakar Červinka, an inspiring mentor of one of us (P. K.).
Th e title com poun d 7 h as been syn th esized in a racem ic form , usin g Suzuki couplin g (8 +
15 → 16) as th e key step. Pure en an tiom er (S)-(–)-7 h as been obtain ed by carbon ylation of
th e kn own brom ide (S)-(+)-12 followed by reduction of th e resultin g m eth yl ester (S)-(+)-18
with LiAlH4.
Keyw ord s: Biaryls; Bin aph th yls; Axially ch iral ligan ds; Alcoh ols; Ph en ols; Suzuki-Miyaura
cross-couplin g; NOBIN; Asym m etric reduction s.
Th e classical 2,2′-disubstituted 1,1′-bin aph th alen es1 (Ch art 1), such as th e
h om obiden tate BINOL 2 (1) an d BINAP 3 (2), an d h eterobiden tate NOBIN 4,5
(3), MOP 6 (4), an d MAP 4i,7 (5), are establish ed ligan ds for gen eratin g ch iral
tran sition m etal catalysts th at are utilized in asym m etric reaction s.
2
2
1
1
X
Y
OH
X
1'
2'
1'
8'
1, X = Y = OH
6, X = NH2
7, X = CH2OH
2, X = Y = PPh2
3, X = NH2, Y = OH
4, X = OMe, Y = PPh2
5, X = NMe2, Y = PPh2
CHART 1
Collect. Czech. Chem. Commun. (Vol. 68) (2003)
doi:10.1135/cccc20030907

908
Vyskočil et al.:
Recen tly, we h ave reported on th e n ovel substitution pattern in th e
1,1′-bin aph th yl realm , with substituen ts in 2,8′-position s, in particular
iso-NOBIN (6), an d th eir application in asym m etric catalysis8. iso-NOBIN
was syn th esized via Suzuki couplin g of boron ic acid 8 with dibrom ide 9,
followed by Hartwig–Buch wald am in ation 4h (10 → 11) an d rem oval of th e
protectin g groups8 (Sch em e 1). En an tiom erically pure iso-NOBIN (S)-(–)-6
was prepared from in term ediate 12 th at was resolved in to en an tiom ers. Th e
absolute con figuration of th is n ew series was establish ed by X-ray crystal-
lograph y8. We h ave also dem on strated h igh con figuration al stability of th e
2,8′-disubstituted 1,1′-bin aph th alen es, wh ich is in th e sam e ran ge as th at of
th e classical 2,2′-disubstituted 1,1′-bin aph th alen es8.
Br Br
OMe
Br
Pd(0)
+
OMe
B(OH)2
8
9
10
BBr3 MeI
Ph2C=NH
Pd(0)
1. BBr3
2. H3O+
OMe
OH
Br
OH
NH2
N
CPh2
11
12
6
SCHEME 1
In th is approach , th e key Suzuki couplin g proved to be a difficult step,
sin ce on ly th e dibrom ide 9 was successfully coupled with boron ic acid 8.
Attem pted an alogous couplin g of 8 with th e correspon din g brom o deriva-
tives carryin g a Lewis basic group in th e peri-position , such as 1-am in o-
8-brom on aph th alen e or 1-acetam ido-8-brom on aph th alen e, proved un suc-
cessful an d on ly a slow reduction of th e C–Br bon d was observed. Reversed
polarity, i.e., usin g th e correspon din g 1-boron ic acid with a Lewis-basic
substituen t in 8-position , was also fruitless. For furth er discussion , see ref.8
Havin g com pleted th e syn th esis of iso-NOBIN 6, we en visaged th at a syn -
th esis of th e 2,8′-isom er of BINOL would be desirable. At th is poin t, m olec-
ular m odelin g sh owed th at wh en th e poten tially coordin atin g substituen t
is directly attach ed to 8-position of th e n aph th alen e m oiety, th e expected
Collect. Czech. Chem. Commun. (Vol. 68) (2003)

Synthesis of 2-Hydroxy-8′-(hydroxymethyl)-1,1′-binaphthalene
909
biden tate com plex O–M–X would be too strain ed, so th at ch elation be-
com es un likely. On th e oth er h an d, wh en a spacer is in troduced between
8-position of th e n aph th alen e an d th e ligatin g group, such as th e CH2 group
in 7, th e geom etry appeared m uch m ore favorable for th e ch elation .
In th e syn th esis of 7, we plan n ed to em ploy th e Suzuki couplin g as a key
step. Sin ce aryl iodides are kn own to be m ore reactive th an th e correspon d-
in g brom ides9, we iden tified iodoester 15 (Sch em e 2) as a suitable electro-
ph ilic partn er for th e couplin g with boron ic acid 8. To th is en d, th e com -
m ercially available ben zoin dolon e 13 was h ydrolyzed (NaOH, MeOH–H2O
1:1, reflux, 20 h ) an d th e resultin g, un stable am in o acid was im m ediately
subjected to San dm eyer reaction (HCl, NaNO2, –5 °C, 15 m in ; th en NaI,
0 to 50 °C)10,11, wh ich gave rise to th e iodo acid 14 (43% overall). Ester-
ification of th e latter acid (CH2N2, Et2O, 0 °C) afforded th e required iodo es-
ter10 15 (98%) as a fairly stable com poun d. Attem pts at Suzuki couplin g of
th e latter iodo derivative 15 with boron ic acid 8 un der our stan dard con di-
tion s em ployed for th e preparation of 10 (Pd(PPh 3)4, Na2CO3, DME–water,
reflux) proved fruitless, as th e reaction led to h ydrolysis an d deh alogen -
ation of th e startin g iodo ester 15. On th e oth er h an d, th e use of th e recen t
Buch wald protocol12, design ed for sim ple arom atic brom o an d iodo esters,
was successful. Un der th ese con dition s (Pd(dba)2, dpePh os, K3PO4, toluen e,
110 °C, 36 h ), th e desired 2,8′-disubstituted bin aph th yl 16 was obtain ed in
good yield (59%). Altern atively, th e latter ester was also prepared by th e
palladium -catalyzed carbon ylation of m eth oxy brom ide 10 (CO, (AcO)2Pd,
dppf, MeOH, Et3N, reflux 24 h ; 69%). Deprotection of 16 (BBr3, CH2Cl2,
room tem perature, 2 h ) furn ish ed lacton e 17 (76%) rath er th an th e expect-
O
I
CO2R
HN
1. NaOH, H2O
2. NaNO2, HCl
OMe
CO2Me
8, Pd(0)
3. NaI
4. CH2N2
14, R = H
13
BBr3
O
15, R = Me
(±)-16
CO, MeOH
(AcO)2Pd
dppf
OMe
CH2OH
LiAlH4
O
10
(±)-17
(±)-7
SCHEME 2
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910
Vyskočil et al.:
ed h ydroxy ester13. Lacton e 17 was th en con verted in to th e racem ic iso-
h om o-BINOL (±)-7 on stan dard reduction (LiAlH4, THF, room tem perature,
overn igh t; 92%). To date, we were n ot able to fin d a suitable m eth od for
resolution of (±)-7 (or its precursors) in to en an tiom ers. A sm all am oun t of
th e latter diol was resolved via HPLC of th e correspon din g dim en th yl car-
bon ate, prepared from (±)-7 by th e reaction with (–)-m en th yl ch loroform -
ate (2 equivalen ts). However, th is m eth od is h ardly suitable for large-scale
operation s.
An altern ative m eth od, wh ich also allowed to establish th e absolute con -
figuration of 7, com m en ced with th e palladium (0)-catalyzed carbon ylation
(Sch em e 3) of (S)-(+)-12 (≥99% ee)8 in m eth an ol (CO, MeOH, (AcO)2Pd
(6 m ole %), dppp, reflux, 24 h ), wh ich afforded m eth yl ester (S)-(+)-18
(71%), wh ose reduction (LiAlH4, THF, room tem perature, overn igh t) pro-
duced th e desired BINOL an alogue (S)-(–)-7 (96%). In terestin gly, carryin g
out th e latter reaction at reflux rath er th an at room tem perature, led to th e
com plete reduction of th e ester group, affordin g th e m eth yl derivative14
(S)-(+)-19.
CO
OH
Br
OH
CO2Me
MeOH
(AcO)2Pd
(S)-(+)-12
(S)-(+)-18
LiAlH4
LiAlH4, THF
reflux 24 h
rt, 16 h
OH
CH3
OH
CH2OH
(S)-(+)-19
(S)-(−)-7
SCHEME 3
In con clusion , a n ew an alogue of BINOL, n am ely diol 7, with th e n ovel
2,8-disubstitution pattern , h as been syn th esized in both racem ic an d
en an tiom erically pure form . Th e syn th esis of th e racem ate relied on th e
Suzuki couplin g of boron ic acid 8 with iodo ester 15 as th e crucial step, fol-
lowed up by m an ipulation of th e fun ction al groups (Sch em e 2). Th e key
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Synthesis of 2-Hydroxy-8′-(hydroxymethyl)-1,1′-binaphthalene
911
steps in th e syn th esis of en an tiopure (S)-(–)-7 in volved th e Suzuki couplin g
of th e sam e boron ic acid (8) with peri-dibrom ide 9 (Sch em e 1), resolution of
th e h ydroxy brom ide8 12, an d carbon ylation of (S)-(+)-12 (Sch em e 3). Th e
absolute con figuration of th e fin al diol 7 follows from th e previously estab-
lish ed8 con figuration of 10 an d 12. Application s of th is n ovel diol in asym -
m etric catalysis will be reported in due course.
EXPERIMENTAL
Gen eral Meth ods
Meltin g poin ts were determ in ed on a Kofler block an d are un corrected. Boilin g poin ts (b.p.)
of com poun ds obtain ed by kugelroh r (bulb-to-bulb) distillation correspon d to un corrected
air bath tem peratures. Optical rotation s were recorded in CHCl3 at 25 °C un less oth erwise
in dicated with an error less th an ±0.1. Th e [α]D values are given in 10–1 deg cm 2 g–1. Th e
NMR spectra (δ, ppm ; J, Hz) were recorded in CDCl3, 1H at 400 MHz an d 13C at 100.6 MHz
with CDCl3-d1 (δ 7.26, 1H; δ 77.0, 13C) as in tern al stan dard un less oth erwise in dicated. Vari-
ous 2D-tech n iques an d DEPT experim en ts were used to establish th e structures an d to assign
th e sign als. Th e IR spectra (ν, cm –1) were recorded for a th in film between KBr plates or for
CHCl3 solution s or in a solid by th e Golden Gate tech n ique. Th e m ass spectra (EI an d/or CI)
were m easured on a dual sector m ass spectrom eter usin g direct in let an d th e lowest
tem perature en ablin g evaporation . All reaction s were perform ed un der an atm osph ere of dry,
oxygen -free n itrogen (or argon wh ere specified) in oven -dried glassware twice evacuated an d
filled with th e n itrogen . Solven ts an d solution s were tran sferred by syrin ge-septum an d can -
n ula tech n iques. All solven ts for th e reaction s were of reagen t grade an d were dried an d dis-
tilled im m ediately before use as follows: dieth yl eth er from lith ium alum in um h ydride;
tetrah ydrofuran (THF) from sodium /ben zoph en on e; dich lorom eth an e from calcium h ydride.
Stan dard workup of an eth ereal solution m ean s wash in g 3× with 5% HCl (aqueous), water,
an d 3× with 5% KHCO3 (aqueous) an d dryin g with MgSO4. Petroleum eth er refers to th e
fraction boilin g in th e ran ge of 40–60 °C. Yields are given for isolated products sh owin g on e
spot on a TLC plate an d n o im purities detectable in th e NMR spectrum . Th e iden tity of th e
products prepared by differen t m eth ods was ch ecked by com parison of th eir NMR, IR, an d
MS data an d by th e TLC beh avior.
(±)-8′-Hydroxym eth yl-1,1′-bin aph th alen -2-ol (±)-(7)
LiAlH4 (114 m g, 3 m m ol) was added to a solution of lacton e (±)-17 (296 m g, 1 m m ol) in dry
THF (5 m l) an d th e resultin g m ixture was stirred at room tem perature overn igh t. Th e reac-
tion was quen ch ed with saturated aqueous Na2SO4 solution (10 m l), acidified with 5% aque-
ous HCl (5 m l), an d extracted with CH2Cl2 (3 × 10 m l). Th e com bin ed organ ic extracts were
dried over an h ydrous MgSO4, filtered, an d evaporated un der reduced pressure. Th e crude
product was purified by flash ch rom atograph y on silica gel (30 g) usin g toluen e, followed by
a toluen e–eth yl acetate m ixture (4:1) as eluen t to afford pure (±)-7 (276 m g, 92%) as a
viscous oil. 1H NMR (400 MHz, CDCl3): 4.04 (d, J = 14.1, 1 H); 4.29 (d, J = 14.1, 1 H); 5.00
(s, 1 H); 7.01 (dm , J = 8.4, 1 H); 7.22–7.27 (m , 1 H); 7.30 (d, J = 8.8, 1 H); 7.30–7.35 (m , 1 H);
7.43 (dd, J = 6.9 an d 1.4, 1 H); 7.51–7.57 (m , 1 H); 7.62 (dd, J = 8.2 an d 7.00, 1 H); 7.66
Collect. Czech. Chem. Commun. (Vol. 68) (2003)

912
Vyskočil et al.:
(dm , J = 7.2, 1 H); 7.85 (dm , J = 8.0, 1 H); 7.90 (dd, J = 9.0 an d 0.8, 1 H); 7.96 (dd, J = 8.5
an d 1.5, 1 H); 8.06 (dd, J = 8.2 an d 1.4, 1 H). 13C NMR (100 MHz, CDCl3): 63.79 t, 117.52 d,
122.92 s, 123.64 d, 124.55 d, 125.66 d, 126.13 d, 127.04 d, 127.26 d, 128.20 d, 128.79 s,
129.51 d, 129.81 s, 130.09 d, 130.78 s, 130.83 d, 132.17 d, 134.01 s, 135.65 s, 137.70 s,
150.37 s. IR (CHCl3): 3538 (OH), 1621 an d 1598 (arom .), 1468 (CH2), 1055 (C–O). MS, m/z
(%): 300 (M• +, 14), 282 (23), 281 (23), 266 (22), 265 (100), 253 (28), 252 (23), 239 (10), 126
(15), 119.5 (7). HRMS (EI): for C21H16O2 calculated 300.1150, foun d 300.1148.
(S)-(–)-8′-Hydroxym eth yl-1,1′-bin aph th alen -2-ol (S)-(–)-(7)
Ester (S)-(+)-18 (100 m g, 0.3 m m ol) in dry THF (5 m l) was stirred with h eatin g un til a clear
solution was obtained. The solution was cooled to room tem perature, LiAlH4 (23 m g, 0.6 m m ol)
was added, an d th e resultin g m ixture was stirred overn igh t at th e sam e tem perature. Th e re-
action was quen ch ed by stirrin g with crystallin e Na2SO4·10H2O (200 m g) for 5 m in . Th e
th ick m ixture was th en filtered th rough silica gel (5 g), th e adsorben t was wash ed with
m eth an ol (3 × 10 m l), an d th e solven t was evaporated un der reduced pressure to afford diol
(S)-(–)-7 (88 m g, 0.3 m m ol, 96%) as a foam : m .p. 81–82 °C (CHCl3); [α]D –2.4 (c 5.0, CHCl3).
8-Iodo-1-n aph th oic Acid (14)
1H-Ben zo[cd]in dol-2-on e (13; 16.9 g, 0.1 m ol) was suspen ded in a solution of NaOH (10 g,
0.25 m ol) in aqueous m eth an ol (1:1, 200 m l). Th e m ixture was refluxed for 20 h , th en
cooled to room tem perature, an d con cen trated HCl (50 m l, 0.6 m ol) was slowly added11
.
Th e m ixture was cooled to –5 °C an d NaNO2 (10 g, 0.145 m ol) was slowly added, th e m ix-
ture was stirred for 15 m in an d a solution of urea (8.4 g, 0.14 m ol) in water (50 m l) was
added, followed by a solution of NaI (30 g, 0.2 m ol) in water (100 m l). Th e resultin g m ix-
ture was stirred at 0 °C for 1 h , th en at 20 °C for 2 h , an d fin ally at 50 °C for 2 h . Th e prod-
uct was taken up in to toluen e (4 × 100 m l), th e organ ic extract was wash ed with 10%
aqueous Na2S2O3 (2 × 50 m l), brin e (50 m l), dried over an h ydrous MgSO4, filtered, an d
evaporated un der reduced pressure. Th e crude product was purified by flash ch rom atograph y
on silica gel (150 g) usin g ch loroform as eluen t to give crude iodo acid 14 (13.3 g, 43%).
Th is m aterial was purified by crystallization from a 1:1 water–m eth an ol m ixture (100 m l) to
give th e pure iodo acid10 14 (10.8 g, 35%).
Meth yl 8-Iodo-1-n aph th oate (15)
8-Iodo-1-n aph th oic acid (8.9 g, 0.03 m ol) was dissolved in dieth yl eth er (200 m l) an d cooled
to 0 °C. An eth eral soulution of fresh ly m ade diazom eth an e (m ade from Diazald, 12.8 g,
0.06 m ol) was th en added an d th e m ixture was stirred at 0 °C for 1 h . Th e diazom eth an e ex-
cess was quen ch ed with acetic acid (3 g) an d th e solven ts were rem oved un der reduced pres-
sure. Th e residue was purified by flash ch rom atograph y on silica gel (100 g) usin g toluen e–
eth yl acetate 5:1 as eluen t to give th e pure iodo ester10 15 (9.17 g, 98%).
(±)-Meth yl (2-Meth oxy-1,1′-bin aph th alen yl)-8′-carboxylate (±)-(16)
Method A. An oven -dried Sch len k tube was filled with Pd(dba)2 (184 m g, 0.4 m m ol,
10 mole %), dpePhos 12 (258 m g, 0.48 m m ol, 12 m ole %), iodo ester 15 (1.25 g, 4 m m ol),
boron ic acid 8 (1.62 g, 8 m m ol), an d K3PO4 (2.55 g, 12 m m ol). Activated 4Å m olecular
Collect. Czech. Chem. Commun. (Vol. 68) (2003)

Synthesis of 2-Hydroxy-8′-(hydroxymethyl)-1,1′-binaphthalene
913
sieves were th en added, th e tube was filled with argon , dry toluen e was added (20 m l), an d
th e resultin g m ixture was h eated at 110 °C for 36 h . Th e m ixture was th en diluted with
water, th e organ ic ph ase was separated, an d th e water ph ase was extracted with eth yl acetate
(2 × 20 m l). Th e com bin ed organ ic extracts were dried over an h ydrous MgSO4, filtered, an d
evaporated un der reduced pressure. Th e crude product was purified by flash ch rom atogra-
ph y on silica gel (30 g) usin g toluen e as eluen t to give pure (±)-16 (807 mg, 59%): m.p.
164–165 °C (AcOEt). 1H NMR (400 MHz, CDCl3): 2.45 (s, 3 H); 3.73 (s, 3 H); 7.30–7.36 (m ,
3 H); 7.41–7.52 (m , 4 H); 7.63 (dd, J = 8.2 an d 6.9, 1 H); 7.81–7.84 (m , 1 H); 7.90 (dd, J = 9.1
an d 0.8, 1 H); 7.96 (dd, J = 8.2 an d 1.3, 1 H); 8.03 (dd, J = 7.3 an d 2.2, 1 H). 13C NMR
(100 MHz, CDCl3): 50.87 q, 56.24 q, 113.36 d, 123.49 d, 123.57 s, 124.45 d, 125.64 d,
126.02 d, 126.51 d, 127.17 d, 127.63 d, 128.38 s, 128.45 d, 129.05 s, 129.56 d, 131.34 d,
131.64 d, 132.04 s, 133.30 s, 134.19 s, 134.38 s, 154.33 s, 170.57 s. IR (CHCl3): 1720 (CO),
1271. MS, m/z (%): 342 (M• +, 100), 295 (22), 252 (32), 239 (27), 83 (15). HRMS (EI):
for C23H18O3 calculated 342.1256, foun d 342.1255.
8
Method B. A stirred solution of (±)-10 (200 m g, 0.5 m m ol), (AcO)2Pd (16 m g, 0.07 m m ol),
1,1′-bis(diph en ylph osph in o)ferrocen e (72 m g, 0.13 m m ol) an d trieth ylam in e (0.4 m l) in dry
m eth an ol (2.0 m l) was h eated to 65 °C un der an atm osph ere of carbon m on oxide (from a
ballon ) for 24 h . Th e m ixture was th en cooled to room tem perature an d th e solven t was
evaporated un der reduced pressure to afford a brown residue. Th e crude product was puri-
fied usin g flash ch rom atograph y on a silica gel colum n (5 g) with toluen e as th e eluen t to
afford (±)-16 (120 m g, 0.35 m m ol, 64%) as a wh ite solid, iden tical with th e com poun d ob-
tain ed by m eth od A: m .p. 164–165 °C (AcOEt).
Lacton e (±)-17
Boron tribrom ide (4.2 m l of 1 M solution in CH2Cl2) was slowly added to a solution of th e
bin aph th yl derivative (±)-16 (684 m g, 2 m m ol) in dry CH2Cl2 (10 m l) at 0 °C. Th e m ixture
was stirred at 0 °C for 2 h an d quen ch ed with brin e (20 m l). Th e organ ic ph ase was sepa-
rated an d th e aqueous ph ase was extracted with CH2Cl2 (2 × 10 m l). Th e com bin ed organ ic
extracts were dried over an h ydrous MgSO4, filtered, an d evaporated un der reduced pressure.
Th e residue was purified by flash ch rom atograph y on silica gel (30 g) usin g toluen e as
eluen t to give pure (±)-17 (450 m g, 76%) as a viscous oil. 1H NMR (400 MHz, CDCl3):
7.38–7.48 (m , 2 H); 7.62 (dd, J = 8.1 an d 7.2, 1 H); 7.62 (d, J = 8.8, 1 H); 7.73 (dd, J = 8.1
an d 7.3, 1 H); 7.81 (dm , J = 8.5, 1 H); 7.90 (dm , J = 8.0, 1 H); 7.96 (dm , J = 8.5, 1 H); 7.97
(dd, J = 7.3 an d 1.2, 1 H); 8.04 (dd, J = 8.2 an d 1.4, 1 H); 8.18 (dd, J = 8.4 an d 1.4, 1 H); 8.56
(dd, J = 7.2 an d 1.4, 1 H). 13C NMR (100 MHz, CDCl3): 121.23 d, 125.06 d, 125.39 d,
125.48 d, 125.87 d, 126.43 s, 126.79 d, 127.06 s, 128.49 d, 129.32 d, 130.65 s, 131.17 d,
131.39 s, 132.57 s, 132.84 s, 133.11 d, 134.26 s, 135.26 d, 135.40 d, 147.29 s, 166.50 s.
IR (CHCl3): 1735 (C=O), 1604 (arom .). MS, m/z (%): 296 (M• +, 76), 294 (18), 269 (22), 268
(100), 252 (9), 251 (9), 240 (10), 239 (46), 237 (19), 148 (6), 134 (6), 133 (5), 120 (10), 119.5
(32), 119 (11), 118.5 (19), 106.5 (9). HRMS (EI): for C21H12O2 calculated 296.0837, foun d
296.0833.
Meth yl (S)-(+)-2-Hydroxy-1,1′-bin aph th alen e-8′-carboxylate (S)-(+)-(18)
A solution of (S)-(+)-12 (640 m g, 1.8 m m ol; ≥99% ee 8), (AcO)2Pd (40 m g, 0.2 m m ol),
1,1′-bis(diph en ylph osph in o)ferrocen e (195 m g, 0.3 m m ol) an d trieth ylam in e (1.2 m l) in dry
m eth an ol (6.0 m l) was h eated to 65 °C wh ile stirrin g un der an atm osph ere of carbon m on -
Collect. Czech. Chem. Commun. (Vol. 68) (2003)

914
Vyskočil et al.:
oxide (from a ballon ) for 24 h . Th e m ixture was cooled to room tem perature an d th e solven t
was evaporated un der reduced pressure to afford a brown residue. Th e crude product was pu-
rified usin g flash ch rom atograph y on a silica gel colum n (5 g) with dich lorom eth an e, fol-
lowed by a dich lorom eth an e–m eth an ol m ixture (80:1) to furn ish (S)-(+)-18 (426 m g,
1.3 m m ol, 71%) as a wh ite solid: m .p. 236–237 °C (CH2Cl2); [α]D +5.7 (c 1.4, CHCl3).
1H NMR (400 MHz, DMSO): 2.46 (s, 3 H); 7.22–7.29 (m , 3 H); 7.38–7.41 (m , 3 H); 7.52–7.55
(m , 1 H); 7.66–7.70 (m , 1 H); 7.80–7.85 (m , 2 H); 8.07 (dd, J = 8.3 an d 1.2, 1 H); 8.15 (dd,
J = 8.3 an d 1.3, 1 H); 9.46 (s, 1 H). 13C NMR (100 MHz, DMSO): 50.83 t, 118.60 s, 120.17 q,
120.68 s, 124.89 s, 125.02 s, 126.37 s, 126.53 s, 127.09 s, 127.97 s, 128.28 q, 128.46 s,
129.33 s, 129.71 q, 131.40 s, 131.83 s, 132.44 q, 133.97 q, 134.42 q, 134.62 q, 152.96 q,
169.68 q. IR (solid): 3371 (OH), 1705 (C=O), 1273. MS, m/z (%): 328 (M• +, 25), 83 (100), 268
(66), 239 (30), 196 (21), 47 (19). HRMS (EI): for C22H16O3 calculated 328.1099, foun d
328.1098.
(S)-(+)-8′-Meth yl-1,1′-bin aph th alen -2-ol (S)-(+)-(19)
A stirred m ixture of ester (S)-(+)-18 (180 m g, 0.55 m m ol) an d LiAlH4 (42 m g, 1.1 m m ol) in
dry THF (5 m l) was refluxed for 24 h . Th e reaction m ixture was cooled to 0 °C an d
quen ch ed by stirrin g with crystallin e Na2SO4·10H2O (200 m g) for 5 m in . Th e th ick m ixture
was th en filtered th rough silica gel (5 g), wh ich was th en wash ed with eth er (3 × 30 m l).
Th e solven t was evaporated un der reduced pressure an d th e residue was purified by flash
ch rom atograph y on a silica gel colum n (5 g) with a petroleum eth er–dieth yl eth er m ixture
(10:1) to afford (S)-(+)-19 (105 m g, 0.37 m m ol, 67%) as a brown solid: m .p. 128–129 °C
(CHCl3); [α]D +0.9 (c 3.3, CHCl3). 1H NMR (400 MHz, CDCl3): 3.13 (s, 3 H); 4.77 (s, 1 H);
6.95 (d, J = 8.3, 1 H); 7.10–7.23 (m , 4 H); 7.29–7.33 (m , 2 H); 7.48 (t, J = 7.1, 1 H); 7.72–7.77
(m , 3 H); 7.91 (dd, J = 8.2 an d 1.1, 1 H). 13C NMR (100 MHz, CDCl3): 22.99 s, 117.57 s,
123.71 s, 123.98 q, 125.45 s, 125.85 s, 126.16 q, 126.47 s, 127.08 s, 128.34 s, 129.00 q, 129.94 s,
130.51 s, 131.13 s, 132.08 s, 132.82 q, 134.82 q, 135.80 q, 136.04 q, 150.77 q. IR (solid):
3502, 3433 (OH). MS, m/z (%): 284 (M• +, 55), 269 (30), 268 (13), 239 (12), 85 (65), 83 (100).
HRMS (EI): for C21H16O calculated 284.1201, foun d 284.1200).
We thank NATO (administered by the Royal Society) for a fellowship to Dr. Š. Vyskočil, EPSRC and
GSK for a CASE award to S. C. Lockhardt, Grant Agency of the Czech republic for grant No.
203/01/D051, Grant Agency of the Charles University for grant No. 243/20B CH, and Ministry of Ed-
ucation, Youth and Sports of the Czech Republic for the project MSM 113100001.
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11. The intermediate 8-amino-1-carboxylic acid is unstable and must be submitted to the
next step immediately.
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leading to a ring closure at C-1 has been observed in the BINOL (1), MAP (5), and
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11002.
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