2-Phenyl-1-boraadamantane complexes. Crystal structure and use in the synthesis of cage compounds

Article abstract of DOI:10.1023/A:1020991729668

Complexes of 2-phenyl-1-boraadamantane with trimethylamine and pyridine were studied by X-ray diffraction analysis. The 2-phenyl-1-boraadamantane adduct with tetrahydrofuran (1) was transformed to 1-hydroxy-2-phenyladamantane via a carbonylation - oxidation sequence. The intramolecular version of the organoborane reaction with organic azides was employed as a key step in the transformation of 2-phenyl-1-boraadamantane adduct (1) into 2-phenyl-1-azaadamantane (5).

Full text of DOI:10.1023/A:1020991729668

1562
Russian Chemical Bulletin, International Edition, Vol. 51, No. 8, pp. 1562—1567, August, 2002
2ꢀPhenylꢀ1ꢀboraadamantane complexes.
Crystal structure and use in the synthesis of cage compounds
b
b
M. E. Gurskii,a V. А. Ponomarev,а D. G. Pershin,а Yu. N. Bubnov,а,b M. Yu. Antipin, and К. А. Lyssenko
ꢀ
aN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (095) 135 5328
bA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (095) 135 5085
Complexes of 2ꢀphenylꢀ1ꢀboraadamantane with trimethylamine and pyridine were studꢀ
ied by Xꢀray diffraction analysis. The 2ꢀphenylꢀ1ꢀboraadamantane adduct with tetrahydrofuꢀ
ran (1) was transformed to 1ꢀhydroxyꢀ2ꢀphenyladamantane via a carbonylation—oxidation
sequence. The intramolecular version of the organoborane reaction with organic azides was
employed as a key step in the transformation of 2ꢀphenylꢀ1ꢀboraadamantane adduct (1) into
2ꢀphenylꢀ1ꢀazaadamantane (5).
Key words: boraadamantanes, 2ꢀphenylꢀ1ꢀboraadamantane, 1ꢀhydroxyꢀ2ꢀphenylꢀ
adamantane, 2ꢀphenylꢀ1ꢀazaadamantane, Xꢀray study, amine complexes, carbonylation—oxiꢀ
dation, iodination, azides, cyclization.
Recently, we reported1 the synthesis of 2ꢀphenylꢀ1ꢀ
According to Xꢀray diffraction data, complexes 2
and 3 crystallize as racemates. It should be noted that for
complex 2, seldom encountered quasiꢀracemic crystals
are formed. Adduct 2 crystallizes in the chiral noncentroꢀ
symmetric space group P21 but the crystallographically
independent molecule is a superposition of two enantiꢀ
omers in which the 1ꢀboraadamantane fragments are
turned with respect to one another through 45° around
the B—N bond (Fig. 1). This means that the crystal
contains both enantiomers in 1 : 1 ratio.
boraadamantane complexes 1—3, in one of which
throughꢀspace interaction of the substituent in position 2
with the ligand, trimethylamine molecule, was clearly
manifested. In particular, for 2ꢀphenylꢀ1ꢀboraadamantane
complex with trimethylamine (2), steric inhibition of
free rotation of the Ph group was found by dynamic 13C
1
and H NMR spectroscopy, and the activation paramꢀ
eters of the rotation were calculated. In this work, we
report the results of Xꢀray diffraction study of 2ꢀphenylꢀ
1ꢀboraadamantane complexes with trimethylamine (2)
and pyridine (3); the transformation of 1ꢀboraadamantane
cage into the adamantane and 1ꢀazaadamantane cage
was carried out.
Unfortunately, the disordered structure of complex 2,
resulting in rather high correlations, precludes deꢀ
tailed analysis of the structure of the 1ꢀboraadamantane
fragment.
Adducts 2 and 3 were prepared from tetrahydrofuran
complex 1 on treatment with Me3N and Py, respecꢀ
tively1 (Scheme 1).
The structural features of the complex with Py (3)
(Fig. 2) could be studied in more detail. This compound
is characterized by clearꢀcut steric interaction between
the ligand and the phenyl substituent.
As in the previously studied complexes of unsubꢀ
stituted 1ꢀboraadamantane2 and 2,2´ꢀethylenebisꢀ1ꢀ
boraadamantane with Py3, distortion of the boraadaꢀ
mantane fragment was noted for structure 3 (Tables 1, 2);
in particular, the B(1)—C(2) and B(1)—C(9) bonds are
elongated (1.640(4) and 1.636(4) Å, respectively) with
respect to the B(1)—C(8) bond (1.618(4) Å) and the
B—C—C bond angles (the mean value is 110.1°) are
greater than the C—C—C angles (the mean value
is 106.6°). Yet another feature is elongation of the
C(2)—C(3), C(9)—C(5), and C(8)—C(7) side bonds,
Scheme 1
L = Me3N (2), Py (3)
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1437—1441, August, 2002.
1066ꢀ5285/02/5108ꢀ1562 $27.00 © 2002 Plenum Publishing Corporation

2ꢀPhenylꢀ1ꢀboraadamantane complexes
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 8, August, 2002
1563
C(11)
C(13)
C(12)
C(17)
C(19)
C(18´)
N(1)
C(17´)
C(18)
C(16)
C(19´)
C(15)
C(14´)
C(16´)
B(1)
C(8)
C(2´)
C(9)
C(5)
C(14)
C(15´)
C(8´)
C(2)
C(9´)
C(3´)
C(3)
C(7´)
C(4)
C(10´)
C(5´)
C(7)
C(4´)
C(6)
C(6´)
C(10)
Fig. 1. General view of molecule 2.
whose lengths range from 1.543(3) to 1.563(3) Å (the
mean value is 1.553 Å), with respect to the bonds in the
C(3)C(4)C(5)C(6)C(7)C(10) sixꢀmembered ring, which
vary in the 1.517(4)—1.540(4) Å range (the mean value
is 1.530 Å).
The B(1)—N(1) bond length in the adduct with Py (3)
is 0.045 Å shorter than that in adduct 2; this is in full
agreement with the results of comparison of the stability
of triorganoborane adducts with tertiary amines and pyꢀ
ridine.4
C(13)
C(14)
Due to the presence of the phenyl substituent
in position 2 of complex 3, the pyridine ring is
C(12)
Table 1. Selected bond lengths (d) in structures 2 and 3
C(11)
C(20)
Bond
d/Å
C(15)
2*
3
N(1)
C(21)
B(1)
C(19)
B(1)—N(1)
B(1)—C(2)
B(1)—C(8)
B(1)—C(9)
C(2)—C(3)
C(3)—C(4)
C(3)—C(10)
C(4)—C(5)
C(5)—C(6)
C(5)—C(9)
C(6)—C(7)
C(7)—C(8)
C(7)—C(10)
1.691(2)
1.646(3)
1.640(4)
1.618(4)
1.635(3)
1.563(3)
1.538(3)
1.524(4)
1.540(4)
1.517(4)
1.543(3)
1.536(3)
1.548(3)
1.537(3)
C(18)
1.624(5) [1.654(5)]
1.628(7) [1.596(6)]
1.669(6) [1.667(6)]
1.581(8) [1.563(9)]
1.552(9) [1.506(9)]
1.52(1) [1.525(9)]
1.58(1) [1.499(9)]
1.52(1) [1.56(1)]
1.53(1) [1.559(8)]
1.55(1) [1.52(1)]
1.55(1) [1.547(8)]
1.55(1) [1.48(1)]
C(8)
C(16)
C(2)
C(17)
C(9)
C(7)
C(6)
C(10)
C(3)
C(4)
C(5)
* The bond lengths for the second enantiomer are given in
brackets.
Fig. 2. General view of molecule 3.

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Gurskii et al.
Table 2. Selected bond angles (ω) in structures 2 and 3
tion (Scheme 2). The yield of 1ꢀhydroxyꢀ2ꢀphenylꢀ
adamantane (4) was 47%.
Angle
ω/deg
2*
3
Scheme 2
C(2)—B(1)—N(1)
C(8)—B(1)—N(1)
C(8)—B(1)—C(2)
C(8)—B(1)—C(9)
C(9)—B(1)—N(1)
C(9)—B(1)—C(2)
C(3)—C(2)—B(1)
C(4)—C(3)—C(2)
C(10)—C(3)—C(2)
C(10)—C(3)—C(4)
C(3)—C(4)—C(5)
C(4)—C(5)—C(9)
C(6)—C(5)—C(4)
C(6)—C(5)—C(9)
C(5)—C(6)—C(7)
C(6)—C(7)—C(8)
C(6)—C(7)—C(10)
C(10)—C(7)—C(8)
C(7)—C(8)—B(1)
C(5)—C(9)—B(1)
C(3)—C(10)—C(7)
112.3(2) [112.4(2)]
108.7(3) [109.4(2)]
106.8(4) [109.7(4)]
108.9(3) [104.7(3)]
108.9(3) [110.4(3)]
111.2(3) [111.2(3)]
106.3(4) [104.6(4)]
112.0(5) [113.6(5)]
110.6(5) [109.4(6)]
107.5(5) [109.2(6)]
111.0(5) [111.5(5)]
110.4(5) [110.1(4)]
105.3(6) [111.4(6)]
112.7(6) [112.1(6)]
112.3(7) [108.8(6)]
112.4(7) [106.4(6)]
106.3(6) [112.1(6)]
109.0(7) [111.2(6)]
108.6(4) [110.0(4)]
107.6(4) [107.4(4)]
111.5(5) [111.4(6)]
111.0(2)
110.8(2)
114.0(2)
107.7(2)
106.4(2)
106.4(2)
105.0(2)
110.0(2)
111.0(2)
109.5(2)
110.5(2)
109.1(2)
109.3(2)
110.8(2)
111.1(2)
108.7(2)
110.2(2)
109.8(2)
107.0(2)
107.9(2)
111.7(2)
Previously, we developed an efficient method for the
transformation of 1ꢀboraadamantanes into the correꢀ
sponding 1ꢀazaadamantanes6 based on the intramolecuꢀ
lar version of the reaction of organoboranes with organic
azides, resulting in secondary amines. The application of
this method to 2ꢀphenylꢀ1ꢀboraadamantane afforded
2ꢀphenylꢀ1ꢀazaadamantane (5), difficult to synthesize,
in a moderate yield.
*The bond angles for the second enantiomer are given in
brackets.
turned relative to the boraadamantane bisecting plane
(B(1)C(2)C(3)C(6)) through 25°. The angle between the
rootꢀmeanꢀsquare planes of the Ph group and the pyriꢀ
dine ring is equal to 76.4°. Due to these positions of
pyridine and 1ꢀboraadamantane cage, the H(11)...H(2)
and H(15)...H(8A) distances are shortened to 2.19 and
2.10 Å, respectively. The observed conformation of comꢀ
plex 3 indicates that the steric repulsion between the
phenyl group and the pyridine ligand predominates over
the repulsion between the H atoms located in the pyriꢀ
dine orthoꢀpositions and the αꢀpositions of the 1ꢀboraꢀ
adamantane fragment.
The transformation 1 → 5 is accomplished as a twoꢀ
pot procedure using simple and readily available reagents
(Scheme 3).
Scheme 3
We carried out the transformation of the 2ꢀphenylꢀ1ꢀ
boraadamantane complex with tetrahydrofuran (1) into
1ꢀhydroxyꢀ2ꢀphenyladamantane (4) and 2ꢀphenylꢀ1ꢀ
azaadamantane (5).
Consecutive carbonylation and oxidation of 1ꢀboraꢀ
adamantane derivatives is among the best methods for
the synthesis of 1ꢀadamantanol derivatives.5
Reagents and conditions: i. NaN3. ii. I2, 90 °C. iii. NaOH,
H2O2. iv. SOCl2. v. NaOH.
Carbonylation of complex 1 was carried out in two
steps. First, a solution of compound 1 in THF was heated
in an autoclave with CO (100 atm) for 3 h at 140 °C.
Then ethylene glycol was added to the reaction mixture
(to facilitate migration of the "third group"), and the
mixture was heated for an additional 3 h at 140 °C under
a CO pressure of 75 atm. The intermediate ethylene
glycol ester 6 was immediately oxidized without isolaꢀ
The first step is the synthesis of bicyclic amino alcohols
7 and 8. The possible mechanism for their formation is
presented in Scheme 4.
The iodination of complex 1 in the presence of a
threefold excess of NaN3 in diglyme at 85 °C is accomꢀ
panied by N2 evolution and affords (after treatment of
the reaction mixture with an alkaline hydrogen peroxꢀ
ide) a mixture (1 : 3) of regioisomeric bicyclic amino

2ꢀPhenylꢀ1ꢀboraadamantane complexes
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 8, August, 2002
1565
Scheme 4
Scheme 6
alcohols 7 and 8, which were separated by column chroꢀ
matography on SiO2 (Scheme 4). The products were
formed as thick gradually crystallizing oils.
The second step, namely, cyclization of individual
amino alcohols 7 and 8 (or their mixture) to give
azaadamantane 5, was attained by refluxing them with
SOCl2 in benzene followed by treatment of the resulting
hydrochloride with NaOH (Scheme 5).
Scheme 5
for the synthesis of difficultly accessible cage compounds
of the adamantane and azaadamantane series.
Experimental
All operations with organoboron compounds were carried
out under dry argon. 1H, 13C, and 11B NMR spectra were
recorded on Bruker ACꢀ200P (200.13, 50.32, and 64.21 МHz,
respectively) and Bruker АМХꢀ400 (400.13 (1H) and
100.13 МHz (13C)) spectrometers in CDCl3. Mass spectra (EI)
were recorded on a KRATOS MS30 instrument (200 eV).
The 2ꢀphenylꢀ1ꢀboraadamantane—tetrahydrofuran (1),
2ꢀphenylꢀ1ꢀboraadamantane—trimethylamine (2), and 2ꢀpheꢀ
nylꢀ1ꢀboraadamantane—pyridine (3) adducts were synthesized
by a procedure published previously.1
2ꢀPhenylꢀ1ꢀadamantanol (4). A solution of complex 1
(9.89 g, 35 mmol) in 70 mL of THF was heated in an autoclave
with CO (initial pressure 100 atm) for 3 h at 140 °C. The
autoclave was cooled, and 5 mL of ethylene glycol was added
to the reaction mixture. The mixture was heated at 140 °C
under a CO pressure of 70 atm for an additional 4 h. The
content of the autoclave was transferred into a flask, and at
0 °C, a mixture of 30 mL of EtOH and 16 mL of 10% NaOH
was added, and 45% H2O2 (4 mL, 50 mmol) was added dropwise.
The mixture was kept for 8 h and refluxed for 10 h, THF was
evaporated, and the residue was extracted with Et2O (2×20 mL)
and chromatographed on SiO2 (Et2O—hexane, 3 : 1, as the
eluent) to give 3.72 g (47%) of compound 4, m.p. 53—55 °C.
Found (%): C, 83.64; H, 8.80. C16H20O. Calculated (%):
2ꢀPhenylꢀ1ꢀazaadamantane (5) is a colorless thin
1
fluid. Its structure was confirmed by the data of H and
13C NMR spectroscopy, mass spectrometry, and elemenꢀ
tal analysis.
We attempted to carry out the cyclization 8 → 5
in a mixture of glacial AcOH with concentrated
HCl by a known procedure.7 However, under these
conditions, the 1ꢀazaadamantane cage was not
formed but dehydration of alcohol 8 took place
to give compound 9 containing a benzylidene group
(Scheme 6).
Thus, 2ꢀphenylꢀ1ꢀboraadamantane readily prepared
from benzylacetylene can serve as the starting compound

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Gurskii et al.
1
C, 84.15; H, 8.83. H NMR, δ: 1.30—2.40 (m, 13 H, adamanꢀ
tane nucleus); 3.07 (s, 1 H, CHPh); 7.40 (m, 5 H, Ph).
13C NMR, δ: 30.2 and 30.9 (C(5), C(7)); 30.8 (C(4)); 36.5
(C(3)); 36.6 (C(9)); 38.9 and 39.9 (C(6), C(10)); 47.7 (C(8));
56.6 (C(2)); 77.0 (C(1)); 125.8 (pꢀC, Ph); 127.8 and 129.6
(oꢀC and mꢀC, Ph); 141.8 (iꢀC, Ph). MS, m/z (Irel (%)):
227 [M]+ (100).
B. A solution of SOCl2 (2.6 mL) in 20 mL of benzene was
added with stirring over a period of 0.5 h to a solution of a
mixture of compounds 7 and 8 (2.47 g, 10.67 mmol) in 40 mL
of benzene. The mixture was stirred for 0.5 h at 20 °C, refluxed
for 4 h, and workedꢀup by the standard procedure for amine
isolation to give 0.6 g (2.8 mmol, 27%) of compound 5, b.p.
105 °C (0.03 Torr), nD20 1.5582. Found (%): C, 84.10; H, 9.31.
C15H19N. Calculated (%): C, 84.06; H, 9.41. The 1H and
13C NMR spectra were identical to those presented in the
previous procedure. MS, m/z (Irel (%)): 213 [M]+ (60).
7ꢀBenzylideneꢀ3ꢀazabicyclo[3.3.1]nonane (9). Glacial AcOH
(16 mL) was added with stirring to a solution of compound 8
(0.21 g, 0.97 mmol) in 16 mL of concentrated HCl. The extract
was neutralized with NaOH to pH 10 and extracted with Et2O
(3×20 mL). The organic layers were combined and dried with
Na2SO4, and the solvent was evaporated. Sublimation (70 °C,
2 Torr) gave 0.12 g (0.56 mmol, 58%) of compound 9, m.p.
44 °C (0.03 Torr). Found (%): C, 82.97; H, 9.81. C15H19N.
Calculated (%): C, 84.06; H, 9.41. 1H NMR, δ: 0.80—3.40 (m,
12 H, H bicyclic fragment); 5.56 (br.s, 1 H, CHPh); 7.10—7.40
(m, 5 H, Ph). 13C NMR, δ: 29.6 (C(1), C(5)); 30.3 (C(9));
34.2 (C(6), C(8)); 44.3 (C(2), C(4)); 125.0, 126.0 (C(10), pꢀC);
128.3, 128.7 (oꢀC, mꢀC); 140.2, 141.4 (C(7), iꢀC). MS,
m/z (Irel (%)): 213 [M]+ (64).
7ꢀHydroxymethylꢀ2ꢀphenylꢀ3ꢀazabicyclo[3.3.1]nonane (7)
and 7ꢀ(αꢀhydroxybenzyl)ꢀ3ꢀazabicyclo[3.3.1]nonane (8). Comꢀ
plex 1 (0.97 g, 38.8 mmol) in 22 mL of diglyme and I2 (9.83 g,
38.8 mmol) in 43 mL of diglyme were added simultaneously
from two dropping funnels over a period of 1.5 h to a suspenꢀ
sion of NaN3 (7.77 g, 119.5 mmol) in 63 mL of diglyme stirred
at 80—85 °C. The mixture was stirred for 0.5 h at the same
temperature (during this period, 930 mL of N2 evolved (80%)).
The solvent was evaporated in vacuo (35—40 °C, 1 Torr) and
the residue was extracted with Et2O (3×30 mL). The combined
ethereal extracts were cooled to 0 °C, 60 mL of 10% NaOH
was added, and 15 mL of 30% H2O2 was added with stirring.
The mixture was stirred for 0.5 h at 0 °C and for 0.5 h at 20 °C
and refluxed for 4 h. The ethereal layer was separated and
extracted successively with 30 mL of 10% HCl and water
(2×50 mL). The aqueous extract was neutralized by NaOH to
pH 10 and extracted again with Et2O (3×20 mL). The organic
layers were combined and dried with Na2SO4, the solvent was
evaporated, and the residue (3.75 g, 42%) was chromatographed
on SiO2 (MeOH—NH4OH, 15 : 1, as the eluent) to give comꢀ
pounds 7 and 8.
Xꢀray diffraction study of compounds 2, 3. Single crystals
suitable for Xꢀray diffraction analysis were prepared by slow
evaporation from solutions in CDCl3 (adduct 2) or by recrysꢀ
tallization from hexane (adduct 3). The main crystallographic
data and refinement parameters for structures 2 and 3 are listed
in Table 3. The structures were solved by the direct method and
refined in the anisotropicꢀisotropic fullꢀmatrix approximation
over F 2. The H atoms in complex 3 were identified from differꢀ
ence electron density syntheses, whereas in complex 2, these
7ꢀHydroxymethylꢀ2ꢀphenylꢀ3ꢀazabicyclo[3.3.1]nonane (7).
Yield 1.49 g (16.5%), thick oil, Rf 0.75. Found (%): C, 77.50;
H, 9.47. C15H21ON. Calculated (%): C, 77.54; H, 9.54.
1H NMR, δ: 1.25—3.90 (m, 15 H, H bicyclic fragment);
7.10—7.49 (m, 5 H, Ph). 13C NMR, δ: 26.1, 30.2 (C(1), C(5));
23.1, 30.5, 32.4 (C(6), C(8), C(9)); 32.1 (C(7)); 48.5 (C(4));
61.1 (C(2)); 69.3 (HCOH); 126.3, 127.8, 126.7, 140.6 (Ph).
MS, m/z (Irel (%)): 231 [M]+ (72).
Table 3. Crystallographic data and structure refinement paꢀ
rameters for 2 and 3
7ꢀ(αꢀHydroxybenzyl)ꢀ3ꢀazabicyclo[3.3.1]nonane (8). Yield
0.29 g (5%), m.p. 73—75 °C, Rf 0.50. Found (%): C, 77.49;
H, 9.57. C15H21ON. Calculated (%): C, 77.54; H, 9.54.
1H NMR, δ: 1.25—1.70 (m, 3 H, H(6)ax, H(8)ax, H(9)ax);
1.75—7.49 (m, 6 H, H(6)eq, H(8)eq, H(9)eq, H(1), H(5), H(7));
2.65—2.85 (q, 4 H, 2 CH2N); 4.10—4.30 (br.s, 2 H, OH, NH
(residual)); 4.60 (s, 1 H, CHOHPh); 7.11—7.41 (m, 5 H,
Ph). 13C NMR, δ: 25.8, 26.2 (C(1), C(5)); 26.5, 28.5, 30.7
(C(6), C(8), C(9)); 36.1 (C(7)); 52.6 (C(2), C(4)); 78.9
(HCOHPh); 126.2, 127.8, 126.5, 145.2 (Ph). MS, m/z (Irel (%)):
231 [M]+ (76).
Parameter
2
3
Molecular formula
M
C18H28B1N1
269.22
C20H24B1N1
289.21
Space group
Radiation
Scan mode
Diffractometer
T/K
a/Å
b/Å
c/Å
P21
P21/n
MoꢀKα (λ = 0.71072 Å)
θ/2θ
«Syntex P21»
193
8.291(5)
9.950(4)
6.539(3)
24.001(9)
94.61(3)
1556.5(12)
4
2ꢀPhenylꢀ1ꢀazaadamantane (5). А. A solution of SOCl2
(1.73 mL) in 15 mL of benzene was added with stirring over a
period of 0.5 h to a solution of compound 7 (1.65 g, 7.13 mmol)
in 25 mL of benzene. The mixture was stirred for 0.5 h at
20 °C, refluxed for 4 h, and workedꢀup by a standard procedure
for amine isolation. The residue (0.5 g) as a thick liquid was
chromatographed on SiO2 (Et2O—NH4OH, 99 : 1, as the eluꢀ
ent) to give 0.312 g (1.46 mmol, 20%) of compound 5,
11.167(4)
8.685(3)
100.09(4)
791.7(6)
2
β/deg
V/Å3
Z
dcalc/g cm–3
2θmax/deg
The number of
independent reflections
(over F for reflections
with I > 2σ(I ))
wR2 (over F 2 for
all reflections)
1.129
66
1.234
50
20
nD 1.5579. Found (%): C, 84.10; H, 9.31. C15H19N. Calcuꢀ
3079
2738
lated (%): C, 84.06; H, 9.41. 1H NMR, δ: 0.90—4.00 (m, 14 H,
H adamantane cage); 7.10—7.49 (m, 5 H, Ph). 13C NMR, δ:
26.9, 27.2 (C(5), C(7)); 27.9 (C(3)); 30.9 (C(4)); 37.0 (C(6));
38.1 (C(10)); 51.7 (C(9)); 60.7 (C(8)); 60.7 (C(2)); 125.8,
126.4, 128.1, 141.6 (Ph). MS, m/z (Irel (%)): 213 [M]+ (100).
0.0641 (2267)
0.1756 (3041)
0.0641 (1922)
0.1753 (2703)

2ꢀPhenylꢀ1ꢀboraadamantane complexes
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 8, August, 2002
1567
atoms were located geometrically. All calculations were carried
out on a SHELXTL PLUS program package (Ver. 5.0).
2. Yu. N. Bubnov, M. E. Gurskii, D. G. Pershin, K. A.
Lysenko, and M. Yu. Antipin, Izv. Akad. Nauk, Ser.
Khim., 1998, 1818 [Russ. Chem. Bull., 1998, 47, 1771 (Engl.
Transl.)].
3. M. E. Gurskii, D. G. Pershin, V. A. Ponomarev, T. V.
Potapova, M. Yu. Antipin, Z. A. Starikova, and Yu. N.
Bubnov, Izv. Akad. Nauk, Ser. Khim., 2000, 501 [Russ. Chem.
Bull., Int. Ed., 2000, 49, 503 (Engl. Transl.)].
This work was financially supported by the Russian
Foundation for Basic Research (Projects Nos. 02ꢀ03ꢀ
32248, 01ꢀ03ꢀ32465 and 99ꢀ03ꢀ31125а), the State Founꢀ
dation for the Support of Leading Scientific Schools
(Project No. 00ꢀ15ꢀ97378), and the "Integratsia" proꢀ
gram (Project 234).
4. H. C. Brown and R. M. Adams, J. Am. Chem. Soc., 1942,
64, 2557.
5. B. M. Mikhailov, V. N. Smirnov, and I. A. Kasparov,
Izv. Akad. Nauk SSSR, Ser. Khim., 1976, 2302 [Bull.
Acad. Sci. USSR, Div. Chem. Sci., 1976, 25 (Engl. Transl.)].
6. Yu. N. Bubnov, M. E. Gursky, and D. G. Pershin,
J. Organomet. Chem., 1991, 412, 1.
References
1. M. E. Gurskii, D. G. Pershin, V. A. Ponomarev, I. D.
Gridnev, O. L. Tok, and Yu. N. Bubnov, Izv. Akad. Nauk,
Ser. Khim., 2000, 497 [Russ. Chem. Bull., Int. Ed., 2000,
49, 499].
7. Th. Reints and W. N. Specamp, Tetrahedron, 1979, 35, 267.
Received March 7, 2002