Stereoconservative cyanation of [1,1′-binaphthalene]-2,2′-dielectrophiles. An alternative approach to homochiral C2-symmetric [ 1,1′-binaphthalene]-2,2′-dicarbonitrile and its transformations

Article abstract of DOI:10.1135/cccc20000729

The performed study on the cyanation of [1,1′-binaphthalene]-2,2′-diiodide and [1,1′-binaphthalene]-2,2′-diyl ditriflate showed reactions with zinc cyanide catalyzed by palladium phosphane complex in DMF to be the most effective procedures with almost com

Full text of DOI:10.1135/cccc20000729

Stereoconservative Cyanation
729
STEREOCONSERVATIVE CYANATION OF [1,1′-BINAPHTHALENE]-
2
,2′-DIELECTROPHILES. AN ALTERNATIVE APPROACH TO
HOMOCHIRAL C -SYMMETRIC [1,1′-BINAPHTHALENE]-
2
2
,2′-DICARBONITRILE AND ITS TRANSFORMATIONS
1
2,
Peter KASÁK and Martin PUTALA *
Department of Organic Chemistry, Faculty of Natural Sciences, Comenius University,
Mlynská dolina CH-2, SK-842 15 Bratislava, Slovak Republic;
1
2
e-mail: kasak@pobox.sk, putala@fns.uniba.sk
Received February 14, 2000
Accepted April 7, 2000
Dedicated to Professor Otakar Červinka on the occasion of his 75th birthday.
Th e perform ed study on th e cyan ation of [1,1′-bin aph th alen e]-2,2′-diiodide an d [1,1′-bin aph -
th alen e]-2,2′-diyl ditriflate sh owed reaction s with zin c cyan ide catalyzed by palladium
ph osph an e com plex in DMF to be th e m ost effective procedures with alm ost com plete con -
servation of stereogen ic in form ation – affordin g correspon din g h igh ly en an tiom erically en -
rich ed din itrile (from diiodide: 94% yield, 92% ee). Din itrile was successfully tran sform ed
into [1,1′-binaphthalene]-2,2′-dicarboxylic acid and -2,2′-dicarbaldehyde in high yields (84–87%).
Key w ord s: Axial ch irality; Biaryls; Bin aph th yl; C -Sym m etry; Cyan ation ; Aryl h alides;
2
Nickel; Palladium ; Stereoselective reaction s; Triflates.
Cyan ation (cyan odeh alogen ation ) of arom atic h alides is a syn th etically im -
portan t reaction affordin g valuable in term ediates – aren ecarbon itriles. Th e
classic m eth od of cyan ation exploits copper(I) cyan ide at h igh reaction
1
tem peratures . In th e m ean tim e, effective m eth ods h ave been developed for
2
tran sition m etal-catalyzed cyan ation s . Th ese reaction s can be perform ed
un der m ilder con dition s an d allow tran sform ation also of less reactive sub-
strates to cyan ides, in cludin g sterically h in dered h alides, trifluoro-
3
–7
8
m eth an esulfon ates
Com plexes of palladium 3
h ave been widely used as catalysts, but also a cobalt com plex in substoich io-
(triflates), or even m eth an esulfon ates (m esylates).
,4,9–17
5–9,18,19
an d n ickel
with ph osph an e ligan ds
2
0
m etric am oun t was foun d to be effective . Several zin c m ediated
cyan ation s h ave also been reported9 . Wide variety of cyan ation reagen ts
h as been used – alkali m etal cyan ides n eat4
,21
–7,10,18
11
or coated on alum in a or
1
2,13,19
in the presence of the phase transfer agents (crown ethers
or am m onium
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

7
30
Kasák, Putala:
salts14,19) or in the presence of various additives
13,15,20
(most often CuI or zin c
3
,16
14
17
salts), zin c cyan ide
(
, copper(I) cyan ide , trim eth ylsilyl cyanide
2
1
9
TMSCN), tosyl cyanide , and even alkyl cyanides (MeCN and BnCN).
2
2
Syn th esis of n on racem ic C -sym m etric 1,1′-bin aph th alen e derivatives
2
bearin g carbon substituen ts in position s 2 an d 2′ can be accom plish ed by
th ree prin cipal m eth ods:
–
stereoselective couplin g of two 1-h alon aph th alen e un its substituted in
2
3
position 2 by carbon substituen t ,
resolution of racem ic [1,1′-bin aph th alen e]-2,2′-dicarboxylic acid
2
4,25
–
2
6
(
[
1), ([1,1′-bin aph th alen e]-2,2′-diyl)dim eth an ol or 2,2′-bis(brom om eth yl)-
1,1′-bin aph th alen e]27 to stereoisom ers (all th ree were obtain ed by
n on stereoselective couplin g an alogous to th e m eth od m en tion ed above
an d followed by furth er fun ction al group tran sform ation s),
–
stereocon servative Pd-catalyzed m eth oxycarbon ylation 28, Ni-catalyzed
2
9
cross-couplin g reaction with Grign ard reagen t
from easily accessible
en an tiopure [1,1′-bin aph th alen e]-2,2′-diyl ditriflate (2).
Application of th e latter approach for direct cyan ation of accessible
h om och iral bin aph th alen e dielectroph iles (ditriflate 2 or diiodide 3) sh ould
be a m ore effective m eth od for th e syn th esis of [1,1′-bin aph th alen e]-
2
,2′-dicarbon itrile (4). In addition it could serve as a valuable in term ediate
for th e syn th esis of oth er h om och iral 1,1′-bin aph th yl derivatives bearin g
carbon substituen ts in position s 2 an d 2′. Attem pts to apply th is approach
for th e syn th esis of din itrile 4 by Ni-catalyzed cyan ation of en an tiopure
5
ditriflate 2 gave poor yield of th e first on e (10%), th ough m ost probably
en an tiopure (see th e discussion below). Replacem en t of on ly on e triflate
group in position 2 to cyan ide of th e C -sym m etric derivative 5 h as been
1
6
effectively performed (Scheme 1), but presence of sterically demanding diphenyl-
COOH
H+ or HO-
P(O)Ph2
1
2
0 KCN, 5% NiBr2
0% PPh3, Zn
OTf
CN
P(O)Ph2 1) HSiCl3, Et3N
) BH3.THF
MeCN, ∆, 2.5 h
P(O)Ph2
2
3) HCOOH, CH2O
(R)-5
99% yield (R)-6
CH2NMe2
PPh2
62% yield (R)
SCHEME 1
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

Stereoconservative Cyanation
731
phosphoryl group [Ph P(O)–] in position 2′ of 6 decreased th e efficien cy of
2
its subsequen t tran sform ation (reduction an d in particular h ydrolysis).
3
0
Th e effective syn th esis of en an tiopure din itrile 4 h as been reported by
four step procedure from racem ic [1,1′-bin aph th alen e]-2,2′-dicarboxylic
acid (RS)-1 (Sch em e 2). Th e preparation of th e latter in overall 26% yield re-
2
5,31
quired six steps
n aph th alen e.
from com m ercially available 1-brom o-2-m eth yl-
.
MeCN
Me
1
) DCC
2) (S)-1-phenylethan-1-amine
) MeCN
COOH
COOH
COOH
CONH
3
H
Ph
SOCl2
(RS)-1
(S,S) 43% yield, >99% d.e.
1
) NH3
CN
CN
2) SOCl2
COCl
CN
50% yield (S)-4
(S)
SCHEME 2
RESULTS AND DISCUSSION
Meth ods for cyan ation of arom atic h alides an d triflates are kn own to be n ot
very reliable; th e efficien cy of in dividual m eth ods varies depen din g on sub-
strate. Bin aph th yl electroph iles (ditriflate 2 an d diiodide 3) used by us
sh ould be con sidered as m edium electron rich , h igh ly h in dered substrates
(
bulky substituen t in ortho-position ).
Startin g from diiodide 3, we exam in ed basic m eth ods kn own for
cyan ation of arom atic h alides (Sch em e 3, Table I). Classic un catalyzed
cyan ation with excess of copper(I) cyan ide did n ot occur in boilin g DMF
a) 4 KCN, 20% CuI,
10% Pd(PPh3)4,
I
I
THF, ∆, 16 h
CN
CN
I
+
CN
b) 4 Zn(CN)2, 10% Pd(dppf)2,
DMF, 90 oC, 16 h
(S)-3 >96% e.e.
(S)-4
(S)-7
a) 84% yield, 66% e.e.
b) 94% yield, 92% e.e.
traces
2% yield, 98% e.e.
SCHEME 3
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

7
32
Kasák, Putala:
TABLE I
Cyan ation of diiodide 3
a
Isolated, %
Cyan ide
equivalen t
Additive
m ole %
An alogous
to ref.
En try
Catalyst
Solven t
3
4
7
1
2
3
4
5
6
7
8
9
–
–
8 CuCN
–
DMFb
NMPb
DMF
NMP
DMF
DMF
DMF
Ph Me
Ph Me
HMPA
THF
90
6c
–
–
≤2
10
–
1
8 CuCN
–
26
13
–
1
A
A
B
B
A
A
A
D
A
A
A
A
B
C
E
4 CuCN
–
67
85
39
35
60
69
67
93
≤2
65
25c
34
33
22
71
39
34
59
–
14
4 KCN
–
–
4a,10b
2 KCN
4 KCNd
38
40
15
13
9
12
10
5
–
4 KCN
4 18C6e
2 TEBAf
Al O
12a
4 KCN
10
5
12 NaCN
4 KCN
11
2
3
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
0
1g
4 KOH
–
–
15a
4 KCN
20 CuI
84h
16
5
≤2
10
≤2
25
15
17
5
15b,15e
2
3 TMSCN
Bn CN
–
NEt3
17
9
3
400 Zn
Bn CN
THF
4
2 Zn (CN)2
2 Zn (CN)2
2 Zn (CN)2
2 Zn (CN)2
2 Zn (CN)2
2 Zn (CN)2
2 Zn (CN)2
2 Zn (CN)2
2 Zn (CN)2
2 Zn (CN)2
2 Zn (CN)2
3 Zn (CN)2
4 Zn (CN)2
–
–
–
–
–
–
–
–
–
–
–
–
–
32
26
32
18
39
26
16
86
93
79
28
88
94j
5
THF
6
THF
7
THF
8
A
B
B
A
A
B
C
B
B
Dioxan e
Dioxan e
MeCN
DMF
DMFi
DMF
DMF
DMF
DMF
11
13
10
5
9
0
1
2
–
3
3
5
10
26
7
14
4
35
–
5
6g
–
2k
15d
a
Diiodide 3 0.50 m m ol, cyan ide, additive, 10 m ole % (relative to 3) of palladium catalyst; 16 h
b
c
at 90 °C (bath); aqueous work-up; flash chromatography on silica gel. Heated to reflux. Co m -
p lex react io n m ix t u re.
(
6
d
e
f
Cyan id e w as ad d ed p o rt io n w ise.
1 8 -C ro w n -6 . Ben zyl-
g
h
trieth yl)am m on ium ch loride. From (S)-3, >96% e.e. (polarim etry).
66% e.e. (HPLC),
i
j
k
5% ee (polarim etry). 3 d ays. 92% e.e. (HPLC), 95% e.e. (polarim etry). 98% e.e. (HPLC).
A Pd(dba)2 + PPh 3 (1 : 4); B Pd(dba)2 + dppf (1 : 2); C Pd(dba)2 + dppf (1 : 4); D Pd(OAc)2;
E Pd(dba)2 + P(o-tolyl) (1 : 4).
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

Stereoconservative Cyanation
733
(
en try 1). Furth er in crease of tem perature (boilin g NMP) resulted in partial
decom position of th e reaction m ixture (black viscous m ass) an d low yield
of th e desired product 4 (en try 2). Usin g th e palladium com plex Pd(PPh 3)4
at a lower tem perature with th e sam e cyan ation reagen t (en try 3) gave poor
con version of diiodide 3.
Experim en ts usin g alkali m etal cyan ide as a cyan ation reagen t in th e
presen ce of palladium catalyst, an d with out or with various additives
(
crown eth er, am m on ium salt, base, solid support), yielded low to m oderate
con version s of diiodide 3 to target din itrile 4 (en tries 4–10). Mode of th e
cyan ide addition (in on e portion or portion wise) did n ot affect th e results
(
en tries 5, 6). DMF was foun d to be a key solven t for at least partly effective
cyan ation , sin ce th e presen ce of th e m en tion ed additives (en tries 8–10) de-
creased th e yield rem arkably wh en accom pan ied by th e ch an ge of th e sol-
ven t. Th e on ly really effective m eth od for palladium -catalyzed cyan ation of
diiodide 3 with potassium cyan ide required th e presen ce of copper(I) iodide
as cocatalyst (en try 11). Din itrile 4 in h igh yield (84%) an d on ly traces of
th e startin g m aterial 3 an d th e in term ediate 7 were isolated from th e reac-
tion m ixture.
More curious palladium -catalyzed cyan ation m eth ods explorin g tri-
m eth ylsilyl an d ben zyl cyan ides (en tries 12, 13) gave poor con version , or in
th e latter case, a low am oun t of th e desired product in a com plex reaction
m ixture.
Cyan ation with zin c cyan ide in th e presen ce of palladium catalyst
[
Pd(PPh ) , Pd(dppf) ] afforded th e best result (en tries 22, 26) – com plete
3 4 2
con version of diiodide 3 to din itrile 4, an d th e h igh est yield of th e latter
93–94%), alth ough som e optim ization of reaction con dition s was in evita-
(
ble (en tries 14–26). First, DMF was foun d th e m ost suitable am on g th e
tested solven ts (aceton itrile, DMF, dioxan e, THF; en tries 20, 23, 19, 15) un -
der com parable con dition s (h eatin g to reflux or to 90 °C if th e boilin g poin t
of th e solven t is h igh er). Th e use of 1,1′-bis(diph en ylph osph an yl)ferrocen e
(
dppf) an d triph en ylph osph an e (PPh ) as ligan ds to palladium gave com pa-
3
rable results in m ost of th e solven ts (en tries 14/15, 18/19, 21/23). Yields of
th e product were sligh tly h igh er with triph en ylph osph an e. In order to ob-
tain th e sam e result, th e reaction usin g dppf required th ree equivalen ts of
zin c cyan ide in stead of two with PPh 3 (en try 25 vs 21). An excess of dppf
over palladium (Pd : dppf > 1 : 2) in DMF decreased th e con version of
diiodide 3 (en try 24). A lon ger reaction tim e (en try 22) or a h igh er excess of
zin c cyan ide (4 equivalen ts, en try 26) sh ifted th e yield of th e desired prod-
uct above 90%. Tris(2-tolyl)ph osph an e com plex of palladium was th e least
effective of th ose tested (en try 17).
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

7
34
Kasák, Putala:
In all successful cases (except en tries 1, 4, an d 10), sm all am oun ts of in -
term ediate iodon itrile 7 was isolated from th e reaction m ixture, togeth er
with startin g diiodide 3 an d din itrile 4. Th e am oun t of iodon itrile 7 was al-
ways lower th an th at of din itrile 4. Th is observation is well un derstan dable
sin ce iodon itrile 7 sh ould be m ore reactive th an th e startin g diiodide 3 due
to electron ic (electron with drawin g n ature of th e already presen t cyan o
group) an d steric reason s as well (sm all cyan o group com pared with large
iodin e atom ). Products of h ydrodeh alogen ation were n ot detected in an y
reaction .
We failed to fin d a procedure for th e effective cyan ation of ditriflate 2
(
Sch em e 4, Table II). Ditriflate 2 would be a better can didate for practical
application of cyan ation procedure, sin ce it is m ore easily accessible th an
OTf 1.2 Zn(CN) , 10% Pd(dppf)2
CN
CN
OTf
CN
2
+
OTf
DMF, 90 oC, 16 h
(
R)-2
(R)-4
17% yield, 93% e.e.
(R)-8
9
2% e.e.
3% yield
SCHEME 4
TABLE II
Cyan ation of ditriflate 2
a
Isolated, %
Cyan ide
equivalen t
An alogous
to ref.
En try
Catalyst
Solven t
MeCN
2
4
8
1b
2d
3
A
B
B
B
B
2.2 KCN
34
69
61
56
76
10c
17e
16
21
8
40
3
1.2 Zn (CN)2 DMF
1.2 Zn (CN)2f DMF
1.2 Zn (CN)2 DMFg
3a,16a
3c
5
4
5
5
4 Zn (CN)2
DMF
≤2
15d
a
Ditriflate 2 0.50 m m ol, cyan ide, 10 m ole % of catalyst (relative to 2); 16 h at 90 °C (bath );
b
aq u eo u s wo rk-u p ; flash ch ro m at o grap h y o n silica gel. From (R)-2, e.e. was n ot given .
c
d
Claim ed en an tiopure (HPLC), calculated 89% e.e. (polarim etry).
From (R)-2, 92% e.e.
e
f
(
HPLC), >96% e.e. (polarim etry). 93% e.e. (HPLC), 94% e.e. (polarim etry). Cyan ide was
g
added portion wise. 150 °C. A NiBr , 4 PPh , 3 Zn ; B Pd(dba) + dppf (1 : 2).
2
3
2
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

Stereoconservative Cyanation
735
diiodide 3. We did n ot succeed to im prove result of th e m eth od explorin g
potassium cyan ide in th e presen ce of in situ form ed n ickel catalyst (10% of
5
din itrile 4, en try 1 (ref. )), th ough th is m eth od h as been applied for very ef-
6
ficien t tran sform ation of m on otriflate 5 to th e correspon din g n itrile 6. Ob-
served low con version of ditriflate 2 to din itrile 4 was quite surprisin g –
diph en ylph osph oryl group (in position 2′ of m on otriflate 5) sh ould be
sterically m ore dem an din g th an th e secon d triflate group in our case (in 8).
Perh aps an explan ation could be th at th e –P(O)Ph group h as a rem arkable
2
electron with drawal ch aracter in con trast to –OSO CF , but also m ore elec-
2
3
3
d
tron rich aryltriflates h ave been con verted to n itriles . We suppose th at a
probable reason for th e failure of effective cyan ation of ditriflate 2 by n ickel
catalyst sh ould be th at th e partially in troduced first n itrile group coordi-
n ates n ickel com plex an d n ickel th erefore can n ot reach th en th e secon d
triflate position . Th is could also explain wh y in th ese sin gle case m ore of
m on on itrile 8 th an n itrile 4 was obtain ed. Ch an ge of catalyst to palladium
com plex an d cyan ation reagen t to zin c cyan ide did n ot yield a h igh er con -
version of ditriflate 2, but it afforded sligh tly h igh er yield of din itrile 4
(
16–17%, en tries 2, 3). In con trast to th e cyan ation of diiodide 3 in our case
1
5d
an d som e aryl triflates , an excess of zin c cyan ide decreased th e con ver-
sion of ditriflate 2 (en try 5). Th e m ode of th e addition of cyan ation reagen t
(
in on e portion or stepwise) an d perform in g th e reaction at h igh er tem pera-
ture did n ot in fluen ce th e result (en try 2 vs 3 an d en try 4).
Havin g foun d th e optim um procedure for th e syn th esis of din itrile 4
from diiodide 3, we in vestigated stereoch em ical beh avior of axially ch iral
bin aph th alen e m oiety in th e course of th e reaction – wh eth er th e
stereogen ic in form ation would be con served. Th is is th e un ique peculiarity
of th e 2,2′-substituted 1,1′-bin aph th yl derivatives, sin ce th e steric h in -
dran ce of th e groups in position s 2 an d 2′ is crucial for con figuration al
(
(
atropoisom eric) stability of th ese derivatives an d exch an ge of th is groups
especially sim ultan eous) m ay cause racem ization of th e bin aph th yl un it.
2
2,32
We foun d
th at th e Negish i palladium -catalyzed cross-couplin g reac-
tion s in both 2,2′-position s of diiodide 3 proceeds stereocon servatively
stereoselectively), wh ile in th e Suzuki an d Stille couplin gs (with less reac-
(
tive organ om etallics), alm ost full racem ization of bin aph th yl m oiety took
place. Th erefore th e prediction of th e stereoch em ical result was n ot th at
trivial. Startin g from en an tiopure diiodide (S)-3 (>96% ee), we exam in ed
on ly th ose m eth ods wh ich gave h igh yields of din itrile 4 – palla-
dium -catalyzed reaction s with potassium cyan ide as cyan ation reagen t in
th e presen ce of copper(I) iodide (Table I, en try 11) an d with zin c cyan ide
(
Table I, en try 26). Th e form er afforded din itrile 4 with 66% ee. Th is result
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

7
36
Kasák, Putala:
is surprisin g, because on th e basis of th e previous results with
cross-couplin g reaction s, on e would expect extrem e results as m ore proba-
ble (full racem ization for sim ultan eous process or full con servation of
stereogen ic in form ation for stepwise reaction ). Th e latter cyan ation m eth od
(
with zin c cyan ide) yielded h igh ly en rich ed din itrile 4 (92% ee) with alm ost
com plete con servation of stereogen ic in form ation from th e substrate.
Mon on itrile 7 was en an tiopure (98% ee), sin ce its tran sform ation regards
on ly on e of critical position s 2 an d 2′.
Cyan ation of ditriflate (R)-2 with potassium cyan ide in th e presen ce of
n ickel catalyst was reported5 to proceed with com plete con servation of
stereogen ic in form ation givin g (R)-4 (Table II, en try 1; claim ed as
en an tiopure based on HPLC). However, th e given value of specific optical
rotation for (R)-4 com pared with our poin ts to on ly 89% ee. We exam in ed
cyan ation of ditriflate (R)-2 (92% ee) with zin c cyan ide in th e presen ce of
palladium catalyst in DMF (Table II, en try 5) wh ich took place with com -
plete reten tion of con figuration on th e bin aph th alen e m oiety, affordin g
din itrile 4 with 93% ee.
Th e described effective cyan ation procedure (Table I, en try 26) is quite
sim ple an d does n ot require special equipm en t; it can serve as a con ven ien t
route to th e valuable in term ediate to oth er n on racem ic C -sym m etric
2
1
,1′-bin aph th alen e derivatives bearin g carbon substituen ts in position s 2
an d 2′. For th is purpose, we exam in ed tran sform ation s of cyan o groups of
din itrile 4 to oth er fun ction al groups (carboxylic acid, form yl, an d am in o-
m eth yl, Sch em e 5).
1
) SnCl2, HCl, Et2O
r.t., 16 h
1) NaOH, H2O, DEG
140 oC, 30 h
CHO
CHO
CN
CN
COOH
COOH
2) H+
2
) steam, 5 h
84% yield
9
4
87% yield 1
BH3.THF
or LiAlH4
or LiAlH4/AlCl3
or H2/Pd-C
CH2NH2
CH2NH2
SCHEME 5
Alkalin e h ydrolysis of din itrile 4 in dieth ylen e glycol an d th e followin g
acid work-up afforded th e correspon din g dicarboxylic acid 1 in h igh yield
(
87%). Reduction of 4 with an h ydrous tin (II) ch loride in th e presen ce of
HCl followed by h ydrolysis gave dicarbaldeh yde 9 in a very good yield
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

Stereoconservative Cyanation
737
(
84%). Reduction of cyan o group to am in om eth yl on e was n ot successful
with th e boran e com plex BH ·THF (wh ich was used for reduction of
3
6
m on on itrile 6). Reduction with a large excess of LiAlH occurred on ly at el-
4
evated tem perature (in boilin g dioxan e) with LiAlH /AlCl (in refluxin g
4
3
THF) or h ydrogen ation over Pd-C, but in all cases it yielded to com plex re-
action m ixture wh ere on ly traces of desired 2,2′-bis(am in om eth yl)-
[
1,1′-bin aph th alen e] were detected (GC).
EXPERIMENTAL
All cyan ation experim en ts were perform ed in dried deoxygen ated solven ts un der argon at-
3
3
34
35
m osph ere usin g Sch len k tech n ique. Pd(dba) (ref. ), Ni(PPh ) Cl (ref. ), dppf (ref. ),
2
3
2
2
3
6
37
38
ditriflate (RS)-2, (R)-2, diiodide (RS)-3, (S)-3, an d Me SiCN (ref. ) were prepared accord-
3
in g to literature procedures. KCN, Zn (CN) , an d Sn Cl were dried prior to use.
2
2
Meltin g poin ts were m easured on a Kofler block an d are un corrected. IR spectra were
–1
1
recorded on a Specord M 80 spectroph otom eter (waven um bers in cm ) in ch loroform . H NMR
spectra (δ, ppm ; J, Hz) were m easured on a Varian Gem in i 300 (300 MHz) in strum en t in
CDCl3 with tetram eth ylsilan e as in tern al stan dard. Flash colum n ch rom atograph y was per-
form ed on 30–60 µm silica gel an d th in -layer ch rom atograph y (TLC) on Silufol UV 254 foils.
HPLC an alysis was don e on (+)-poly(triph en ylm eth yl)m eth acrylate/silica usin g a Jasco
CD-995 detector (CD an d UV detection ). Specific optical rotation was m easured on a
–
1
Perkin –Elm er 241 polarim eter at tem peratures from 19 to 23 °C an d are given in 10 deg
2
–1
cm
g . Elem en tal an alysis was determ in ed on an Erba Scien ce 1106 in strum en t.
Cyan ation of 2,2′-Diiodo-[1,1′-bin aph th alen e] (3). Gen eral Procedure
Th e flask con tain in g diiodide 3 (253 m g, 0.50 m m ol), cyan ide, additive, 10 m ole % (relative
to 3) of palladium catalyst was flush ed with Ar atm osph ere an d a deoxygen ated dry solven t
(
1
2 m l) was added via syrin ge. Reaction m ixture was stirred an d h eated on a bath at 90 °C for
6 h . Th e solven t was th en rem oved in vacuo, an d dich lorom eth an e (20 m l) was added. Th e
resultin g m ixture was wash ed with 10% aqueous Na CO (10 m l), H O (10 m l), brin e
2
3
2
(
10 m l) an d dried over an h ydrous Na SO . Solven t was evaporated an d th e residue purified
2 4
by flash ch rom atograph y on silica gel, eluen t isoh exan e–dich lorom eth an e (9 : 1) up to
isoh exan e–dich lorom eth an e–dieth yl eth er (9 : 1 : 2). Results are sum m arized in Table I.
Cyan ation of [1,1′-Bin aph th alen e]-2,2′-diyl Bis(trifluorom eth an esulfon ate) (2).
Gen eral Procedure
Th e flask con tain in g ditriflate 2 (259 m g, 0.50 m m ol), cyan ide, 10 m ole % (relative to 2) of
catalyst was flush ed with Ar atm osph ere an d a deoxygen ated DMF (2 m l) was added via sy-
rin ge. Reaction m ixture was stirred an d h eated on th e bath at 90 °C for 16 h . Solven t was
th en rem oved un der vacuum , an d dich lorom eth an e (20 m l) was added. Work-up was th e
sam e as from diiodide 3. Results are sum m arized in Table II.
1,1′-Binaphthalene]-2,2′-dicarbonitrile (4): M.p. 239–241 °C (ref.30: 232 °C). IR: 2 235
30
[
1
(
C≡N). H NMR: 8.12 d, 2 H, J(4,3) = 8.5 (H-4); 8.03 broad d, 2 H, J(5,6) = 8.2 (H-5); 7.85 d,
2
H, J(3,4) = 8.5 (H-3); 7.66 ddd, 2 H, J(6,8) = 1.1, J(6,7) = 6.9, J(6,5) = 8.5 (H-6); 7.44 ddd,
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

7
38
Kasák, Putala:
2
H, J(6,8) = 1.1, J(7,6) = 6.9, J(7,8) = 8.5 (H-7); 7.17 broad d, 2 H, J(8,7) = 8.5 (H-8). TLC:
RF 0.35 (isoh exan e–dieth yl eth er 4 : 1). HPLC separation (eluen t m eth an ol, 15 °C, flow 1.00
–
1
m l m in , λ (UV, CD) 230 n m ); k′: 0.7 (–)-(R)-4, 1.0 (+)-(S)-4. Polarim etry: Table I, en try 11,
α]D +45.5 (c 0.96, CHCl ); Table I, en try 26, [α] +67.0 (c 0.90, CHCl ), +55.6 (c 0.98,
[
3
D
3
6
CH Cl ); Table II, en try 5, [α] –66.0 (c 0.91, CHCl ); ref. , (R)-4: [α] –53.95 (c 1.01,
CH Cl ); ref. , (R)-4: [α]D –70.5 (c 1.00, CHCl ), (S)-4: [α] +68.6 (c 1.54, CHCl ).
2
2
D
3
D
3
0
2
2
3
D
3
2
′-Iodo-[1,1′-binaphthalene]-2-carbonitrile (7): M.p. 225–227 °C. For C21H12IN (405.3) calcu-
lated: 62.23% C, 2.98% H, 3.45% N; foun d: 62.41% C, 3.07% H, 3.39% N. IR: 2 230 (C≡N).
1
H NMR: 8.07 d, 1 H, J = 8.5; 8.06 d, 1 H, J = 8.5; 8.01 broad d, 1 H, J = 8.5; 7.92 broad d,
1
1
H, J = 8.5; 7.80 d, 1 H, J = 8.5; 7.74 d, 1 H, J = 8.5; 7.64 ddd, 1 H, J = 1.2, 7.0, 8.5; 7.50 ddd,
H, J = 1.1, 7.2, 8.5; 7.42 ddd, 1 H, J = 1.2, 7.0, 8.5; 7.27 ddd, 1 H, J = 1.1, 7.2, 8.5; 7.22
broad d, 1 H, J = 8.5; 6.98 broad d, 1 H, J = 8.5. TLC: RF 0.50 (isoh exan e–dieth yl eth er–di-
ch lorom eth an e 8 : 1 : 2). HPLC separation (eluen t h eptan e–isopropan ol 9 : 1, 15 °C, flow
–
1
0
.50 m l m in , λ (UV, CD) 230 n m ); k′: 2.3 (–)-(R)-7, 2.8 (+)-(S)-7. Polarim etry, (S)-7: Table I,
en try 26, [α]D 14.2 (c 0.93, CHCl ).
3
2
′-Trifluoromethanesulfonyloxy-[1,1′-binaphthalene]-2-carbonitrile (8): M.p. 101–105 °C. IR:
1
2
1
7
230 (C≡N). H NMR: 8.16 d, 1 H, J = 8.9; 8.11 d, 1 H, J = 8.9; 8.04 d, 1 H, J = 8.5; 8.01 d,
H, J = 8.5; 7.83 d, 1 H, J = 8.9; 7.71 d, 1 H, J = 8.9; 7.70 d, 1 H, J = 8.9; 7.66–7.44 m , 4 H;
.16 broad d, 1 H, J = 8.5. TLC: RF 0.22 (isoh exan e–dich lorom eth an e 4 : 1).
[
1,1′-Bin aph th alen e]-2,2′-dicarboxylic Acid (1) (An alogous to ref.39
)
Mixture of din itrile 4 (152 m g, 0.50 m m ol), NaOH (90 m g, 2.25 m m ol), an d on e drop of wa-
ter in 1.5 m l of dieth ylen e glycol was stirred at 140 °C for 30 h . After coolin g down , it was
poured in to 20 m l of water. Th e resultin g m ixture was extracted with dieth yl eth er (2 × 15 m l).
To th e aqueous layer, 10% aqueous HCl (15 m l) was added an d th e obtain ed m ixture was
stirred for 1 h . Wh ite precipitate was filtered off un der reduced pressure, wash ed with water to
3
1
n eutral reaction , an d dried. Yield: 148 m g (87%). M.p. 277–279 °C (ref. : 272–274 °C). Spec-
3
1
tra were in good agreem en t with ref.
.
[
1,1′-Bin aph th alen e]-2,2′-dicarbaldeh yde (9) (An alogous to ref.40
)
A m ixture of an h ydrous Sn Cl2 (473 m g, 2.5 m m ol) in absolute dieth yl eth er (2 m l) was satu-
rated with dry HCl an d was slowly stirred at room tem perature for 2 h . A solution of
din itrile 4 (128 m g, 0.43 m m ol) in absolute dieth yl eth er (5 m l) was added to th is m ixture.
Th e color turn ed yellow. Dry HCl was again bubbled th rough th e m ixture for 2 h an d th en
it was allowed to stan d overn igh t. Th e organ ic layer was decan ted an d th e steam was passed
th rough th e residue for 5 h . After coolin g, th e resultin g m ixture was extracted with eth yl
acetate (3 × 20 m l). Com bined organic layers were washed with water (2 × 20 m l), brine (15 m l),
an d th en dried over an h ydrous Na SO . Evaporation of solven t gave 108 m g (84%) of 10 as
2
4
4
1
a yellowish crystallin e solid. M.p. 125–129 °C (ref. : 124–126 °C). Spectra were in good
4
1
agreem en t with ref.
.
This work was supported by the Slovak Grant Agency for Science (grant No. 1/7013/20). The au-
thors are thankful to Prof. A. Mannschreck and Mrs N. Pustet (University of Regensburg, Germany) for
performing HPLC analysis.
Collect. Czech. Chem. Commun. (Vol. 65) (2000)

Stereoconservative Cyanation
739
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