The first preparation of (1S,5R)-(-)- and (1R,5S)-(+)-7-phenyl-3- borabicyclo[3.3.1]non-6-enes and their application for synthesis of chiral cyclohexene derivatives

Article abstract of DOI:10.1016/j.jorganchem.2005.02.036

(1S,5R)-(-)- and (1R,5S)-(+)-7-phenyl-3-borabicyclo[3.3.1]non-6-enes of 97-98% de that differed only by the location of the double bond were prepared by the resolution of diastereomeric intramolecular chelates with l- and d-prolinol. Deboronation of chira

Full text of DOI:10.1016/j.jorganchem.2005.02.036

Journal of Organometallic Chemistry 690 (2005) 2840–2846
www.elsevier.com/locate/jorganchem
The first preparation of (1S,5R)-(ꢀ)- and
(1R,5S)-(+)-7-phenyl-3-borabicyclo[3.3.1]non-6-enes and their
application for synthesis of chiral cyclohexene derivatives
a
M.E. Gurskii , A.L. Karionova , A.V. Ignatenko , K.A. Lyssenko ,
a
a
b
b
M.Yu. Antipin , Yu.N. Bubnov
a,b,
*
a
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991, GSP-1, Leninsky prosp., 47, Moscow, Russia
A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119991, Vavilova str., 28, Moscow, Russia
b
Received 10 December 2004; accepted 16 February 2005
Available online 10 May 2005
Abstract
(1S,5R)-(ꢀ)- and (1R,5S)-(+)-7-phenyl-3-borabicyclo[3.3.1]non-6-enes of 97–98% de that differed only by the location of the dou-
ble bond were prepared by the resolution of diastereomeric intramolecular chelates with L- and D-prolinol. Deboronation of chiral
bicyclic boranes obtained was used for synthesis of optically active 3,5-dimethyl- and 3,5-dihydroxymethyl-1-phenylcyclohexenes.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: 3-Borabicyclo[3.3.1]non-6-ene derivatives; 2,2-Disubstituted 3-borabicyclo[3.3.1]-nonanes; Chiral auxiliaries; Chelate complexes;
Diastereomeric purity
1. Introduction
and/or 2 in enantiomerically pure form for using them
as chiral transfer reagents in asymmetric allyboronation
as well as the precursors for the synthesis of natural and
related compounds.
Indeed, 7-substituted 3-allyl-3-borabicyclo[3.3.1]non-
6-enes 1 and 2 are the compounds of C1 symmetry,
which enantiomers differ only in the location of the
double bond. Previously, the resolution of certain
boracyclanes such as borolanes [3] allylborane [4] and
10-trimethylsilyl-9-borabicyclo[3.3.2]decane (10-TMS-
9-BBD) [5] has been performed via intramolecular com-
plexes with valinol, prolinol or pseudoephedrine.
Herein, we report a methodology for obtaining
The thermal reaction (130–140 ꢁC) of triallylborane
with terminal acetylenes (allylboron–acetylene conden-
sation) gives rise to 7-substituted 3-allyl-3-borabicy-
clo[3.3.1]non-6-enes
treatment of 1 with methanol leads to the corresponding
3-methoxy derivatives 2 [1] (see Scheme 1).
The compounds 1 and 2 have been widely used
as starting materials for the directed stereospecific
synthesis of various cyclic and cage structures such as
cis-3,5-dimethyl-1-cyclohexenes, cis-3,5-dihydroxyme-
thyl-1-cyclohexenes, methylene cyclohexene derivatives
and bis-cyclohexene derivatives [1,2]. However, all the
above compounds were previously obtained only as
racemate. It is desirable to get the bicyclic boranes 1
1 in 70–97% yields. Further
(1S,5R)-(+)
and
(1R,5S)-(ꢀ)-7-phenyl-3-borabicy-
clo[3.3.1]non-6-enes by the resolution of the correspond-
ing diastereomeric intramolecular complexes with L- and
D-prolinol. 3-Borabicyclo-[3.3.1]non-6-enes thus ob-
tained were transformed into optically active cyclohex-
ene derivatives.
*
Corresponding author. Tel.: +7 095 1358951; fax: +7 095 1355328.
E-mail address: bor@ioc.ac.ru (Yu.N. Bubnov).
0022-328X/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.02.036

M.E. Gurskii et al. / Journal of Organometallic Chemistry 690 (2005) 2840–2846
2841
OMe
choice. L- (3a) and D-prolinol (3b) of 98% and 99% enan-
tiomeric purity were used.
)
3 B
B
B
o
130-140
C
MeOH
+
The mixture of two diastereomer complexes (1S,5R)-
4a and (1R,5S)-4b was obtained by the reaction of 1
Ph
Ph
R
C CH
1 (~96%)
1
with 3a (double set of signals was observed in H and
2 (70-97%)
13C NMR) (Scheme 2). Two successive crystallizations
from diethyl ether resulted in (1S,5R)-4a with 96% de,
1
which structure was estimate by H NMR spectroscopy
(Fig. 1).
R = H, Alk, Ph, Alkenyl, OR, etc.
Scheme 1.
2. Results and discussion
An absolute configuration of 3-borabicyclo[3.3.1]-
non-6-ene moiety in compounds 4a was established by
X-ray diffraction analysis on the base of the comparison
with known stereo structure of L-prolinol as a chiral
ligand (Fig. 2).
Racemic 3-methoxy-7phenyl-3-borabicyclo[3.3.1] non-
6-ene ( ) (1) was synthesized in 89% yield by interaction
between triallylborane and phenylacetylene (135–
140 ꢁC) followed by the treatment with methanol [6].
Capacity of diorganylboranes to form air-stable intra-
molecular adducts with 1,2-aminoalcohols was exploited
for resolution of racemate 1.
The conformation of boron containing cycle in 4a is
‘‘distorted chair’’ (the deviations of B(3) and C(9) atoms
˚
are ꢀ0.39 and 0.74 A). Due to the presence of the dou-
ble bond in C(5)C(6)C(7)C(8)C(1)C(9) cycle its confor-
mation is ‘‘distorted sofa’’ with the deviation of C(9)
We tested D-valinol, D-phenylalaninol and D- and L-
prolinol and found prolinols to be chiral auxiliaries of
˚
atom (0.745(2) A). The phenyl ring is almost coplanar
OMe
B
MeO
B
Ph Ph
H
H
( )1
HO
Crystallization
N
H
Crystallization
OH
N
H
Et O
2
Et O
2
L-Prolinol
D-Prolinol
3a
3b
H
H
H
H
O
O
O
O
N
N
N
N
B
B
B
B
H
H
H
H
+
*
*
*
+
*
Ph
Ph
Ph
Ph
*
*
*
*
(1S,5R) - 4d
(1R,5S) - 4b
(1S,5R) - 4a
[α]D18 - 38.17
(1R,5S) - 4c
[α]D + 39.5
20
More
Soluble
More
Soluble
Less
Less
Soluble
Soluble
Scheme 2.
Fig. 1. 1H NMR spectra of 7-phenyl-3-borabicyclo[3.3.1]non-6-ene derivatives with L-prolinol (4a) (200.13 MHz, CDCl3, double bonds signals area).
(a) The starting diastereomer mixture (ꢁ1:1). (b) The product of first crystallization 1S,5R:1R,5S – 3:1. (c) The product of second crystallization –
separate diastereomer form 1S,5R.

2842
M.E. Gurskii et al. / Journal of Organometallic Chemistry 690 (2005) 2840–2846
H
O
N
B
H
Ph
(1S,5R) - 4a
MeOH
HCl/Et O
2
Ph
Ph
OMe
B
-
RCOOH
OH
H2O2
Me
CH2OH
Me
CH2OH
Ph
(3S,5R)-6a
[α]D20 -9.52
(3S,5R)-5a
[α]D20 -22.8
(1S,5R)-1a
[α]D 14
20
Scheme 3.
optical purity not less than that of their precursors
(1S,5R)-4a and (1R,5S)-4c (ca. 96–97%), as soon as oxi-
dation and protolytic cleavage of organoboranes is
known to proceed with retention of configuration, with-
out of racemization or epimerization.
Fig. 2. The general view of 2(R)-2[(1S,5R)7-phebyl-3-borabicy-
clo[3.3.1]non-6-en-3-iloxymethyl]-tetrahydropyrrole (4a). Selected
˚
bond lengths (A): O(1)–B(3) 1.490(5), N(1)–B(3) 1.698(6), C(2)–B(3)
1.618(6), B(3)–C(4) 1.616(6), C(7)–C(8) 1.318(5); bond angles (ꢁ):
C(16)–O(1)–B(3) 107.1(3) C(200)–N(1)–B(3) 109.3(8), C(20)–N(1)–B(3)
131.4(8), C(17)–N(1)–B(3) 105.0(4), O(1)–B(3)–C(2) 109.2(4), O(1)–
B(3)–C(4) 111.8(4), C(2)–B(3)–C(4) 114.4(4), O(1)–B(3)–N(1) 98.4(3),
C(2)–B(3)–N(1) 114.3(4), C(4)–B(3)–N(1) 107.7(4).
The 2,2-dialkyl-3-borabicyclo[3.3.1]nonane present
another interesting member of 3-borabicyclic families
with C1 symmetry suitable for the creation of optically
active organoboron derivatives. This compound is read-
ily obtained from 2,2-dimethyl-1-boradamantane (8).
We have found that THF complex 8 underwent the com-
pletely regiospecific cleavage of unsubstituted intracyclic
B-C bond under action of methanol in the presence
of catalytic amount of pivalic acid and yielded 83% 3-
methoxy-2,2,7a-trimethyl-3-borabicyclo-[3.3.1]nonane 9
with the base of ‘‘sofa’’ with the torsion angle
C(8)C(7)C(10)C(11) equal to 20.5ꢁ. In crystal, the mole-
cules of 4a are assembled into infinite chains due to the
weak N(1)–H(1N). . .O(1) (1 ꢀ x, ꢀ 1/2 + y, 1/2 ꢀ z)
˚
bond (N. . .O 3.319(3) A).
Treatment of (1S,5R)-diastereomer 4a with methanol
and HCl in diethyl ether led to (1S,5R)-3-methoxy-7-
1
(according to H and 13C NMR data) (Scheme 5).
20
D
phenyl-3-borabicyclo[3.3.1]non-6-ene (1a) (½aꢂ ꢀ 14,
The treatment of compound 9 with 8-hydroxyquino-
line gave the intramolecular complex 10, which molecu-
lar and crystal structure was proved by X-ray diffraction
analysis (Fig. 3).
The boron containing cycle in 10 has conformation of
‘‘chair’’ with deviations of B(3) and C(9) atoms by –
MeOH). Oxidation of the latter with hydrogen peroxide
resulted in (3S,5R)-3,5-dihydroxymethyl-1-phenylcyclo-
20
D
hex-1-ene (5a) (½aꢂ ꢀ 22:8, MeOH) in 60% yield, while
20
D
hydrocarbon (3S, 5R)-6a (½aꢂ ꢀ 9:52, hexane) was
synthesized in 78% yield by the protolytic cleavage of
(1S,5R)-1a with butyric acid under reflux (see
Scheme 3).
˚
0.571(2) and 0.762(2) A. In contrast, C(5)C(6)C(7)
C(8)C(1)C(9) cycle has conformation ‘‘boat’’ (deviation
˚
of C(9) and C(7) atoms are 0.707(2) and 0.625(2) A,
The similar simple methodology was utilized for the
20
D
preparation of (1R,5S)-diasteromer 2c (½aꢂ þ 39:5,
respectively) with the methyl group in equatorial posi-
tion. Totally, the 3-borabicyclo[3.3.1]nonane fragment
in 10 may be described as ‘‘chair-boat’’ conformer. The
B(3) atom has distorted tetrahedral configuration with
the decrease of the O(1)B(3)N(1) angle to 97.3(1)ꢁ. The
presence of two methyl groups at C(4) atom lead to
MeOH) using D-prolinol as a chiral auxiliary. Further
oxidation of 2c afforded optically active (3R,5S)-diol
5b, which was transformed into (3R,5S)-3,5-dimethyl-
20
D
1-phenylcyclohex-1-ene (6b) (½aꢂ þ 8:98, hexane) via
the reduction of bis-tosylate 7 with LiAlH4 (Scheme 4).
To our best knowledge, cyclohexene derivatives 5a,
5b and 6a, 6b were prepared in optically active form
for the first time. Attempts to determine their optical
purity for 5a and 5b using europium (III) tris[3-(hepta-
fluoropropylhydroxymethylene)-l-camphorate] and (+)-
and (ꢀ)-phenylethylamine as chiral shift reagents were
fruitless. We suppose, the above products should have
˚
some shortening of the B(3)–C(4) bond (1.628(2) A) in
˚
comparison to B(3)–C(2) one (1.605(2)A). The B(3)–
˚
N(1) bond length (1.637(2) A) in 10 is slightly elongated
in comparison with the corresponding one in 7-endo-
methyl-3-borabicyclo[3.3.1]non-3-yl 8-hydroxyquinoli-
˚
nate (1.607 A) [6] but significantly shorter than the
corresponding value in 4a.

M.E. Gurskii et al. / Journal of Organometallic Chemistry 690 (2005) 2840–2846
2843
H
O
Ph
Ph
N
Ph
B
-
H
H O ,
OH
2
2
LiAlH
Et2O
TsCl
Py
4
*
Ph MeOH
CH2
HO
CH2
*
CH2
OH
CH2
OTs
Me
Me
Ts
O
(1R,5S) - 4c
7
(3R,5S)-5b
(3R,5S)-6b
20
20
20
[α]
+8
[α]
+21.9
[α]
+39.5
D
D
D
Scheme 4.
O
B
N
OMe
Me
Me
N
Me
Me
Me
Me
B
O
B
OH
MeOH, 20˚Ñ
(cat.)
Me CCOOH
3
Me
Scheme 5.
Me
9
8
10
compound 9 into enantiomers with D-valinol, D-phe-
nylalaninol and D- and L-prolinol. Probably, in this case,
the formation of expected chelate product is impossible
because of steric hindrances (due to the presence of two
methyl groups).
3. Conclusion
In conclusion, we proposed a novel method for the
synthesis of the optically active cyclohexene derivatives
using 3-borabicyclo[3.3.1]non-6-ene enantiomers. We
have shown that L- and D-prolinol proved to be the most
favourable choice of reagents for the enantiomeric reso-
lution of borabicyclic derivatives.
4. Experimental
4.1. General
Fig. 3. The general view of (2,2,7a-trimethyl-3-borabicyclo[3.3.1]non-
All operations with organoboron compounds were
carried out under dry argon. The solvents were purified
according to the standard procedures. The optical rota-
tion was measured on a Perkin–Elmer model 341 polar-
imeter. The 1H, 13C, and 11B NMR spectra were
recorded on Bruker AC-200 instrument (200.13, 50.32
and 64.21 MHz, respectively) or Bruker DRX-500
(500.13 and 125.75 MHz). Compound 8 was prepared
according to [7]. L- and D-Prolinol were synthesized as
described in [8].
˚
3-yl)-8-hydroxyquinolinate (10). Selected bond lengths (A): N(1)–
C(13) 1.320(2), N(1)–C(17) 1.359(2), O(1)–C(18) 1.335(2), O(1)–B(3)
1.544(2), N(1)–B(3) 1.637(2), B(3)–C(4) 1.605(2), C(2)–B(3) 1.628(2);
bond angles (ꢁ): C(18)–O(1)–B(3) 111.1(1), O(1)–B(3)–C(4) 112.5(1),
O(1)–B(3)–C(2) 111.3(1), C(4)–B(3)–C(2) 113.8(1), O(1)–B(3)–N(1)
97.3(1), C(4)–B(3)–N(1) 110.0(1), C(2)–B(3)–N(1) 110.8(1).
We expected that some optically active amino alco-
hols as chiral auxiliary might be used for resolution of
compound 9. Unfortunately, we failed to resolve

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M.E. Gurskii et al. / Journal of Organometallic Chemistry 690 (2005) 2840–2846
4.2. (1S,5R)- and (5R,1S)-diastereomers (4a + 4b)
33.79 (C-9), 36.31 (C-8), 48.20 (NH-CH2), 60.40 (CH-
CH2-O), 67.52 (CH2-O), 124.19 (o-Ph), 126.74 (p-Ph),
128.61 (m-Ph), 132.34 (C-7), 134.30 (C-6), 141.78 (ipso-
Ph) ppm.
To a solution of 1 (7.76 g, 34.2 mmol) in diethyl
ether (20 ml) was added solution of L-prolinol
(3.46 g, 34.2 mmol) in diethyl ether (15 ml) and reac-
tion mixture left to stir at room temperature for
0.5 h. The solvent was removed under reduced pres-
sure to yield the air-stable (5R,1S)- and (1S,5R)-diaste-
reomers 4a and 4b (9.42 g), 11B NMR (CDCl3):
d = 7.36 ppm. Anal. Calc. for C19H26BNO (%): C,
76.75; H, 8.88; B, 3.36; N, 4.70. Found (%): C, 77.3;
H, 8.88; B, 3.66; N, 4.74.
4.3. 2(R)-2[(5S,1R)7-Phenyl-3-borabicyclo[3.3.1]non-
6-en-3-yloxymethyl]-tetrahydropyrrole (4c) and 2(R)-
2[(1S,5R)7-Phenyl-3-borabicyclo[3.3.1]non-6-en-3-
yloxymethyl]-tetrahydropyrrole (4d)
The mixture of 4c and 4d was synthesized analo-
gously to the mixture of 4a and 4b from D-prolinol
(4.00 g, 39.5 mmol) in diethyl ether (20 ml) and a solu-
tion of 1 (9.01 g, 39.5 mmol) in diethyl ether (25 ml).
The (1R,5S)-diastereomer 4c (3.49 g, 30%) with (98%
de) was isolated from the diastereomers mixture of
4c + 4d by fractional crystallizations from diethyl ether
4.2.1. 2(R)-2[(1S,5R)7-Phenyl-3-borabicyclo[3.3.1]-
non-6-en-3-yloxymethyl]-tetrahydropyrrole (4a)
The (1S,5R)-diastereomer 4a (2.7 g, 28.6%) with (97%
de) was isolated from the diastereomers mixture of
4a + 4b by fractional crystallizations from diethyl ether
using the sample of 1R,5S-isomer as a seed.
20
D
using the sample of 1S,5R-isomer as
a
seed.
½aꢂ þ 39:5 (c = 1.7, MeOH), m.p. 105–107 ꢁC. The
18
D
1
½aꢂ ꢀ 38:17 (c = 4.2, MeOH), m.p. 105–107 ꢁC.
parameters of H NMR and 13C NMR are identical to
data for (1S,5R )-diastereomer 4a.
1
500.13 MHz; H NMR (CDCl3): d = 0.54 (br. d, 2H,
H-2a, 4a, 2J(H-2a, H-2b) = 14.34 Hz), 0.72 (dd, 2H,
H-2b, 4b, 2J(H-2a, H-2b) = 14.34 Hz, 2J(H-2b, H-
1) = 6.1 Hz), 1.42, 1.88 (m, 2H, NHCH2CH2), 1.57,
2.05 (m, 2H, CH2CH2CH2), 1.69 (br.dd, 2H, H-9syn,
4.4. (1S,5R)-3-Methoxy-7-phenyl-3-borabicyclo[3.3.1]-
non-6-ene (1a)
2
H-9anti, J(H-9syn, H-9anti) = 11.59 Hz), 2.29 (d, 1H,
To the solution of compound 4a (1.13 g, 3.82 mmol)
in a mixture of diethyl ether (10 ml) and MeOH
(0.36 g,11.46 mmol) was cooled and the solution of
HCl (3.67 N, 2.08 ml) in diethyl ether was added. The
reaction mixture was stirred for 3 h. The solvent was
evaporated and the residue was extracted with pentane
(20 ml). Removal of the solvent and distillation of the
H-8b, 3J(H-8b, H-8a) = 17.7 Hz), 2.49 (s, 1H, H-1),
2.65 (s, 1H, H-5), 2.82 (m, 3H, H-8a, NHCH2), 3.49
(br.d, 1H, OCH2), 3.66 (s, 1H, NH). 3.74 (a, 1H,
OCH2CH), 4.2 (m, 1H, OCH2), 6.62 (d, 1H, H-6,
3J(H-6,H-5) = 4.58 Hz), 7.21 (t, 1H, p-Ph, J = 7.02 Hz),
7.31 (t, 2H, m-Ph, J = 7.94 Hz), 7.39 (d, 2H, o-Ph,
J = 7.94 Hz) ppm. 125.75 MHz; 13C NMR (CDCl3):
d = 27.16 (NH-CH2-CH2), 28.47 (C-1), 31.25 (C-5),
32.37 (CH2-CH2-CH), 33.89 (C-9), 36.12 (C-8), 48.30
(NH-CH2), 60.68 (CH-CH2-O), 67.88 (CH2-O), 124.51
(o-Ph), 126.93 (p-Ph), 128.61 (m-Ph), 132.13 (C-7),
134.30 (C-6), 141.78 (ipso-Ph) ppm.
residue gave (0.82 g, 95.9%) of 1a, b.p. 114–115 ꢁC
20
(1.5 mmHg), ½aꢂ ꢀ 14:0 (c = 20.3, MeOH). 11B NMR
D
(CDCl3, d): d = 54.67 ppm. 1H NMR (CDCl3):
d = 0.90–1.39 (m, 5H, H-2a, H-2b, H-4a, H-4b, H-8b),
1.90 (dd, 2H, H-9anti, H-9syn, 2J(H-9syn -H-
9anti) = 11.62 Hz), 2.29 (d, 1H, H-8a, 2J(H-8a, H-
8b) = 16.64 Hz), 2.70 (br.s, 1H, H-1), 2.79 (br.s, 1H,
3
4.2.2. 2(R)-2[(5S,1R)7-Phenyl-3-borabicyclo[3.3.1]-
non-6-en-3-yloxymethyl]-tetrahydropyrrole (4b)
H-5), 3.69 (s, 3H, OMe), 6.21 (d, 1H, H-6, J(H-6, H-
5) = 5.8 Hz), 7.24–7.45 (m, 5H, H-Ph) ppm.
50.32 MHz; 13C NMR (CDCl3): d = 24.30 (C-2), 25.58,
(C-4), 27.43 (C-1), 29.76 (C-5), 32.31 (C-8), 36.62 (C-
9), 52.96 (OMe), 125.16 (o-Ph), 126.63 (p-Ph), 128.16
(m-Ph), 131.35 (C-7), 132.82 (C-6), 142.52 (ipso-Ph)
ppm.
1
500.13 MHz; H NMR (CDCl3): d = 0.54 (br. d, 2H,
2
H-2a, 4a, J(H-2a, H-2b) = 14.34 Hz), 0.72 (dd, 2H, H-
2b, 4b, 2J(H-2a, H-2b) = 14.34 Hz, 3J(H-2b, H-
1) = 6.1 Hz), 1.42, 1.88 (m, 2H, NHCH2CH2), 1.57,
2.05 (m, 2H, CH2CH2CH2), 1.69 (br.dd, 2H, H-9syn,
2
H-9anti, J(H-9syn, H-9anti) = 11.59 Hz), 2.09 (d, 1H,
H-8b, 2J(H-8b, H-8a) = 17.7 Hz), 2.49 (s, 1H, H-1),
2.65 (s, 1H, H-5), 2.82 (m, 3H, H-8a, NHCH2), 3.41
(d, 1H, OCH2, 3J(H-CH2,H-CH) = 9.15 Hz), 3.66 (s,
1H, NH). 3.74 (a, 1H, OCH2CH), 3.98 (m, 1H,
4.5. Cyclohex-1-ene derivatives
4.5.1. (3S,5R)-3,5-cis-Dihydroxymethyl-1-
phenylcyclohex-1-ene (5a)
3
OCH2), 6.41 (d, 1H, H-6, J(H-6,H-5) = 4.58 Hz), 7.21
To a mixture of 1a (0.5 g, 2.2 mmol) in MeOH (2 ml)
and NaOH (10%, 0.78 ml) was added H2O2 (25%,
1.5 ml) under cooling. The resulting solution was stirred
for 6 h and after was heated under reflux for 1 h, then
cooled to room temperature. The solvent was removed,
(t, 1H, p-Ph, J = 7.02 Hz), 7.31 (t, 2H, m-Ph,
J = 7.94 Hz), 7.39 (d, 2H, o-Ph, J = 7.94 Hz) ppm.
125.75 MHz; 13C NMR (CDCl3): d = 27.03 (NH-CH2-
CH2), 28.47 (C-1), 31.31 (C-5), 32.41 (CH2-CH2-CH),

M.E. Gurskii et al. / Journal of Organometallic Chemistry 690 (2005) 2840–2846
2845
the residue was dissolved in THF (5 ml). Precipitate was
filtered off and dried in vacuo and compound 5a (0.29 g,
4.5.5. (3R,5S)-3,5-cis-Di-p-toluenesulfoxymethyl-1-
phenylcyclohex-1-ene (7)
20
D
60%) was obtained, m.p. 122–124 ꢁC, ½aꢂ ꢀ 22:8
To a solution of compound 5b (0.69 g, 3.1 mmol) in
pyridine (10 ml) was added p-toluoenesulfonyl chloride
(1.77 g, 9.3 mmol) at 0 ꢁC and the reaction mixture
was stirred at this temperature for 12 h. Then this mix-
ture was dissolved in ice water (50 ml) and extracted
with benzene (3 · 15 ml). The extracts were combined
and washed with HCl (10%) and dried over Na2SO4. Re-
moval of the solvent and distillation of the residue gave
compound 7 (1.27 g, 90%), m.p. 107–108 ꢁC. Anal. Calc.
for C28H30O6S2 (%): C, 63.85; H, 5.74; S, 12.18. Found
(%): C, 64.58; H, 6.18; S, 11.6. 1H NMR (CDCl3):
1
(c = 1, MeOH). H NMR (CD3OD): d = 0.86–2.60 (m,
intricate multiplet of aliphatic protons), 3.68 (br.s, 4H,
OCH2), 6.06 (s, 1H, H-2), 7.24–7.45 (m, 5H, H-Ph)
ppm. 13C NMR (CDCl3): d = 30.37 (C-6); 32.30 (C-4);
38.40 (C-5); 41.27 (C-3); 67.86 (CH2-CH-CH2-OH);
68.30 (CH-CH-CH2-OH); 126.20 (o-Ph); 126.74 (p-Ph);
127.86 (C-2); 129.21 (m-Ph); 138.65 (C-1); 143.47 (ipso-
Ph) ppm. Anal. Calc. for C14H18O2(%): C, 76.85; H,
8.13. Found (%): C, 77.03; H, 8.31.
2
4.5.2. (3R,5S)-3,5-Dihydroxymethyl-1-phenylcyclohex-
1-ene (5b)
d = 0.96 (dt, 2H, H-4, J = 11.79 Hz), 1.87 (m, 1H, H-
5), 2.11 (m, 1H, H-3), 2.45 (d, 6H, 2Me, J = 5.2 Hz),
2
To a mixture of 4c (1 g, 3.3 mmol) and NaOH
(10%.1.21 ml) was added H2O2(25%, 3 ml) under cool-
ing. Then resulting mixture was extracted with THF
(10 ml). Precipitate was filtered off and dried in vacuo
3.95 (m, 4H, OCH2), 5.76 (s, 1H, H-2), 7.24–7.40 (m,
8H, H-Ts), 7.76–7.83 (m, 5H, H-Ph) ppm. 13C NMR
(CDCl3): d = 21.78 (C-CH3), 28.10 (C-6), 30.33 (C-4),
33.84 (C-5), 36.52 (C-3), 73.64 (C-CH2CHCH2O),
74.15 (C-CHCHCH2O), 122.89, 125.26, 127.55, 128.42,
130.01, 130.08, 132.85, 138.12, 140.86, 145.05 (Ph-, Ts-
moiety) ppm.
and compound 5b (0.69 g, 93%) was obtained, m.p.
20
D
122–124 ꢁC,. ½aꢂ þ 21:9 (c = 1, MeOH). The parame-
1
ters of H NMR and 13C NMR are identical to data
for (1S,5R)-diastereomer 5a.
4.6. 2,2,7a-Trimethyl-3-methoxy-3-borabicyclo[3.3.1]
nonane (9)
4.5.3. (3S,5R)-3,5-cis-Dimethyl-1-phenylcyclohex-1-ene
(6a)
To the compound 1a (0.87 g, 3.8 mmol) was added
butyric acid (0.34 g, 3.8 mmol) and the mixture was
heated under reflux for 9 h and stirred at room temper-
ature for 48 h. The distillation of the residue gave com-
To a solution of THF complex of 2,2-dimethyl-1-
boraadamantane (1.05 g, 4.3 mmol) in tetrahydrofurane
(5 ml) was added MeOH (0.14 g, 4.3 mmol) and pivalic
acid (0.1 g, 0.9 mmol). The reaction mixture was re-
fluxed for 1 h. Removal of the solvent and distillation
of the residue gave compound 9 (0.69 g, 83%), b.p. 75–
77 ꢁC (1.5 mmHg). 500 MHz; 1H NMR (CDCl3):
d = 0.89 (d, 3H, Me-7a, 2J = 4.13 Hz), 0.91 (s, 9H,
pound 6a (0.56 g, 78%), b.p. 50–52 ꢁC (1.5 mmHg),
20
½aꢂ ꢀ 9:52 (c = 1.7, hexane). 1H NMR (CDCl3):
D
d = 0.9–1.05 (m, 2H, CH-CH2-CH), 1.09–1.20 (d, 6H,
2Me, 2J = 6.83 Hz), 1.8–2.6 (m, intricate multiplet of ali-
phatic protons) ppm. 13C NMR (CDCl3): d = 22.00
(CH3); 22.40 (CH3); 29.62 (C-5); 32.21 (C-3); 36.24 (C-
6); 40.41 (C-4); 125.04 (o-Ph); 126.56 (p-Ph); 128.13
(m-Ph); 130.81 (C-2); 135.69 (C-1); 142.24 (ipso-Ph)
ppm.
2
2Me), 0.97 (dd, 1H, H-4a, J(H-4a, H-4b) = 16.39 Hz),
1.04–1.1 (br.m, 2H, H-4b, H-6a), 1.38 (br. s, 1H, H-1),
1.45 (dm, 1H, H-8a, 2J(H-8a, H-8b) = 14.21 Hz), 1.5
(dm, 1H, H-9anti, 2J(H-9anti, H-9syn) = 13.28 Hz),
2
3
1.72 (dt, 1H, H-8b, J(H-8b, H-8a) = 14.21 Hz, J(H-
8b, H-1) = 6.41 Hz), 1.81–1.87 (m, 2H, H-7b, H-9syn),
2
3
4.5.4. (3R,5S)-3,5-cis-Dimethyl-1-phenylcyclohex-1-ene
(6b)
To a solution of LiAlH4(0.42 g, 11.1 mmol) in
1.94 (dt, 1H, H-6b, J(H-6b, H-6a) = 13.52 Hz, J(H-
6b, H-5) = 6.64 Hz), 2.25 (br.s, 1H, H-5), 3.62 (s, 3H,
OMe) ppm. 125.75 MHz; 13C NMR (CDCl3):
d = 23.66, 23.89 (Me-2), 25.97 (C-7), 26.93 (Me-7),
28.52 (C-5), 30.23 (C-9), 34.76 (C-8), 40.43 (C-6),
42.13 (C-1), 53.11 (OMe) ppm. Anal. Calc. for
C12H23BO: C, 74.25; H, 11.94; B, 5.57%. Found: C,
73.99; H, 11.05; B, 5.89%.
diethyl ether (10 ml) the solution of
7 (1.27 g,
2.78 mmol) in THF (10 ml) was added and the reaction
mixture was heated for 10 h. The solvent was removed
and the residue was dissolved in diethyl ether (10 ml).
Then the solution was decomposed by NaOH (15%) un-
der cooling. Precipitate was filtered off, decomposed by
H2SO4 (10%) and extracted with diethyl ether
(3 · 15 ml) The organic extracts were dried over
Na2SO4. The solvent was evaporated and distillation
4.7. (2,2,7a-Trimethyl-3-borabicyclo[3.3.1]non-3-yl)-8-
hydroxyquinolinate (10)
of the residue gave 6b (0.45 g, 87%), b.p. 50–52 ꢁC
To a solution of 9 (0.266 g, 1.3 mmol) in diethyl ether
(4 ml) was added 8-hydroxyquinoline (0.19 g, 1.3 mmol)
in diethyl ether (6 ml) and mixture was stirred for 1 h.
Then the solvent was evaporated and compound 10
20
(1.5 mmHg),. ½aꢂ ꢀ 8:98 (c = 1.5, hexane). The param-
D
1
eters of H NMR and 13C NMR are identical to data
for (1S,5R)-diastereomer 6a.

2846
M.E. Gurskii et al. / Journal of Organometallic Chemistry 690 (2005) 2840–2846
against F2 in anisotropic approximation for non-hydro-
gen atoms. The analysis of Fourier density synthesis in
4a have revealed that C(19) and C(20) atoms are disor-
dered by two positions, which were refined with equal
occupancies. Crystal data and structure refinement
parameters for 4a and 10 are given in Table 1. All calcu-
lations were performed on an IBM PC/AT using the
SHELXTL software [11].
Table 1
Crystal data and structure refinement parameters for 4a and 10
Molecular formula
4a
C19H26BNO
10
C20H26BNO
Formula weight
Colour, shape
Diffractometer
Temperature (K)
Crystal system
Space group
295.22
307.23
Yellow, prism
SMART CCD
120(2)
Colorless, prism
Siemens P3/PC
293(2)
Orthorhombic
P212121
6.7253(4)
Monoclinic
C2/c
˚
a (A)
31.572(8)
8.006(2)
15.379(5)
117.08(2)
3460.9(16)
8(1)
4.9. Supplementary material
˚
b (A)
10.4345(9)
24.076(6)
˚
c (A)
The crystallographic data have been deposited with
the Cambridge Crystallographic Data Center, CCDC
No. 253148 for 4a and No. 253147 for 10. Copies of this
information may be obtained free of charge from: The
Director, CCDC, 12 Union Road, Cambridge, CB2
1EZ, UK (fax: +44 1223 336033; e-mail: deposit@ccdc.
cam.ac.uk or http://www.ccdc.cam.ac.uk).
b (ꢁ)
3
˚
V (A )
1689.6(5)
4(1)
640
Z(Z0)
F(000)
1328
1.179
0.70
qcalc (gcmꢀ1
)
1.161
0.69
Linear absorption,
l (cmꢀ1
)
h Range (ꢁ)
Measured
Unique
2.13–26.03
5964
2.65–27.05
3861
3245 [R(int) = 0.0540]
1252
236
3800 (0.0130)
2093
312
With [I > 2r(I)]
Parameters
Final R(Fhkl): R1
wR2
Acknowledgements
0.0590
0.1720
0.0377
0.0948
This work was supported by the Russian Foundation
for Basic Research (Grant No. 03-03-32214) the Support
of Leading Schools of the President of the Russian
Federation (Grant Nos. 1060.2003.3, 1917.2003.3 and
YC-1209.2003.03) and the Division of Chemistry and
Materyal Sciences (Programme no. 1).
GOF
q
0.950
0.137/ꢀ0.165
0.952
0.138/ꢀ0.146
ꢀ3
˚
max/qmin (e A
)
(0.36 g, 85.5%) was obtained as yellow crystalls, m.p.
1
140–142 ꢁC. H NMR (C6D6): d = 0.79 (s, 3H, Me-2),
2
0.93 (dd, 1H, H-4a, J(H-4a, H-4b)=13.35 Hz), 1.03 (s,
3H, Me-2), 1.83–2.41 (m, intricate multiplet of aliphatic
protons), 2.73 (br.s, 1H, H-5), 6.42–7.66 (m, 6H, intri-
cate multiplet of 8-hydroxyquinolinate fragment). 13C
NMR (C6D6): d = 23.40, 23.72 (Me-2), 26.56 (C-7),
27.20 (Me-7), 27.29 (C-9), 28.60 (C-5), 33.20 (C-8),
38.21 (C-6), 43.09 (C-1), 108.52 (C-50), 110.50 (30),
121.58 (C-70), 128.25 (C-40), 132.62 (C-60), 137.12 (C-
20), 138.49 (C-90), 138.75 (C-10), 159.88 (C-80) ppm.
Anal. Calc. for C20H26BNO (%): C, 78.19; H, 8.53; B,
3.52. Found: C, 78.38; H, 8.63; B, 3.21.
References
[1] B.M. Mikhailov, Yu.N. Bubnov, Organoboron Compounds in
Organic Synthesis, Harwood Academic Science Publishers, Lon-
don, 1984, p. 781.
[2] Yu.N. Bubnov, M.E. Gurskii, A.I. Grandberg, D.G. Pershin,
Tetrahedron 42 (1986) 1079.
[3] S. Masamune, B.M. Kim, J.S. Petersen, T. Sato, S.J. Veenstra, T.
Imai, J. Am. Chem. Soc. 107 (1985) 4549.
[4] R.P. Short, S. Masamune, J. Am. Chem. Soc. 111 (1989) 1892.
[5] J.A. Soderquist, K. Matos, C.H. Burgos, C. Lai, J. Vacquer, J.R.
Medina, in: M.G. Davidson, A.K. Hughes, T.B. Marder, K. Wade
(Eds.), Contemporary Boron Chemistry, Royal Society of Chem-
istry, Chembridge, UK, 2000, p. 472.
4.8. X-ray diffraction
X-ray diffraction experiments were carried out with a
Bruker SMART 1000 CCD area detector for 4a and Sie-
mens P3/Pc for 10 using graphite monochromated Mo
[6] B.M. Mikhailov, K.L. Cherkasova, Izv. Akad. Nauk SSSR Ser.
Khim. (Russ. Chem. Bull.) (1971) 1244 (in Russian).
[7] B.M. Mikhailov, M.E. Gurskii, S.V. Baranin, Yu.N. Bubnov,
M.V. Sergeeva, A.I. Yanovsky, K.A. Potekhin, A.V. Maleev,
Yu.T. Struchkov, Izv. Akad. Nauk SSSR, Ser. Khim. (Russ. Chem.
Bull.) (1986) 1645 (in Russian).
˚
Ka radiation (k = 0.71073 A, x and h/2h-scans for 4a
and 10, respectively). The structures were solved by di-
rect method and refined by the full-matrix least-squares
[8] M.J. McKennon, A.I. Meyers, J. Org. Chem. 58 (1993) 3568.