Unique stereochemistry of 3ꢀborabicyclononanes
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 9, September, 2004
1975
was obtained in a yield of 3.24 g (71.6%), b.p. 115—120 °C
(1.5 Torr), m.p. 27—30 °C. Found (%): C, 85.73; H, 9.73;
B, 4.54. C17H23BO. Calculated (%): C, 85.65; H, 9.71; B, 4.18.
1H NMR (tolueneꢀd8), δ: 0.72 (dd, 2 H, H(2β), H(4β),
7.2—7.25 (m, 4 H, H(oꢀPh), H(mꢀPh)), 7.12 (t, 1 H, H(pꢀPh),
J = 7.2 Hz).
7αꢀPhenylꢀ3ꢀborabicyclo[3.3.1]nonanꢀ3ꢀyl quinolinꢀ8ꢀolate
(8). A solution of 8ꢀhydroxyquinoline (1.38 g, 9.5 mmol) in
Et2O (20 mL) was added to a solution of compound 4 (2.17 g,
9.5 mmol) in Et2O (10 mL). The reaction mixture was stirred for
1 h, the solvent was distilled off in vacuo, and the residue
was recrystallized from Et2O. Compound 8 was isolated in a
yield of 3.10 g (95.6%), m.p. 146—148 °C. Found (%): C, 80.95;
H, 7.09; B, 3.17. C23H24BNO. Calculated (%): C, 81.38; H, 7.05;
B, 3.00. 1H NMR (CDCl3), δ: 0.54 (dd, 2 H, H(2β), H(4β),
3
2JH(2β),H(2α) = 17.41 Hz, JH(2β),H(1) = 5.5 Hz); 1.02 (d, 2 H,
3
(CH2—CH), JH(Y),H(X) = 7.56 Hz); 1.41 (br.d, 1 H, Hsyn(9),
2JH
= 12.37 Hz); 1.49 (d, 2 H, H(2α), H(4α),
(9),H
(9)
syn
2JH(2α),H(2aβn)t=i 17.41 Hz); 1.71 (dm, 1 H, Hanti(9)); 1.87 (dt, 2 H,
2
3
H(6β), H(8β), JH(6β),H(6α) = 13.98 Hz, JH(6α),H(7) = 5.96 Hz);
2.15 (m, 2 H, H(1), H(5)); 2.22 (br.d, 4 H, H(6α), H(8α),
3
3JH(6α),H(7) = 5.96 Hz); 2.84 (m, 1 H, H(7), JH(7),H(6α)
=
3
3
5.96 Hz); 4.70 (dd, 2 H, (CH2=CH), JH(A),H(X) = 10.08 Hz,
3JH(B),H(X) = 17.06 Hz); 5.59 (ddt, 1 H, (CH=CH2), 3JH(X),H(A)
2JH(2β),H(2α) = 13.21 Hz, JH(2β),H(1) = 4.8 Hz); 0.88 (dd, 2 H,
=
H(2α), H(4α), 2JH(2α),H(2β) = 13.21 Hz); 1.32 (br.d, 1 H, Hsyn(9),
10.08 Hz, 3JH(X),H(B) = 17.06 Hz, 3JH(X),H(Y) = 7.56 Hz); 6.93 (t,
1 H, (pꢀPh), 2J = 7.33 Hz); 7.05 (m, 2 H, (mꢀPh)); 7.21 (d, 2 H,
(oꢀPh), 2J = 7.56 Hz).
1,3,5ꢀTrimethylꢀ7αꢀphenylꢀ3ꢀborabicyclo[3.3.1]nonane (5).
Analogously to the synthesis of compound 2, compound 5 was
synthesized from MeMgI (prepared from Mg (0.47 g, 19.5 mmol)
and MeI (2.8 g, 19 mmol)) and 3ꢀmethoxyꢀ1,5ꢀdimethylꢀ7ꢀ
phenylꢀ3ꢀborabicyclo[3.3.1]nonane (4.8 g, 18.7 mmol). The
yield was 3.7 g (82%), b.p. 118—120 °C (1.5 Torr), m.p. 63 °C.
Found (%): C, C, 85.00; H, 10.49; B, 4.50. C17H25B. Calcuꢀ
lated (%): C, 85.16; H, 10.39; B, 4.36.
2JH
(9) = 12.81 Hz); 1.95—2.07 (m, 4 H, H(6α), H(8α),
(9),H
syn
anti
H(6β), H(8β)); 2.12 (dm, 1 H, Hanti(9), 2JH
=
(9),H (9)
12.81 Hz); 2.42 (m, 2 H, H(1), H(5)); 2.87 (tatn,ti1 H, H(7),
3JH(7),H(6α) = 12.82 Hz, JH(7),H(6β) = 5.6 Hz); 7.03 (d, 1 H,
syn
3
H(7´), J = 7.61 Hz); 7.09 (d, 1 H, H(5´), J = 8.01 Hz); 7.18 (t,
1 H, H(oꢀPh)); 7.33 (t, 1 H, H(mꢀPh), J = 7.61 Hz); 7.49 (d,
2 H, H(oꢀPh), J = 7.61 Hz); 7.51 (m, 1 H, H(3´)); 7.59 (t, 1 H,
H(6´), J = 8.01 Hz); 8.24 (d, 1 H, H(4´), J = 8.01 Hz); 8.27 (d,
1 H, H(2´), J = 4.81 Hz).
3ꢀMethylꢀ7ꢀphenylꢀ3ꢀborabicyclo[3.3.1]nonꢀ6ꢀene (11).
A solution of compound 12 (7.96 g, 35.2 mmol) in Et2O (20 mL)
was added to a solution of MeMgI prepared from Mg (0.86 g,
35.3 mmol) and MeI (5 g, 35.3 mmol) in Et2O (30 mL). The
reaction mixture was refluxed for 3 h and then cooled. The
diethyl ether was distilled off. The precipitate was washed
with hexane and filtered off. The filtrate was concentrated
in vacuo and the residue was distilled. Compound 11 was isoꢀ
lated in a yield of 3.48 g (47%), b.p. 126—127 °C (1.5 Torr),
3ꢀtertꢀButylꢀ7αꢀphenylꢀ3ꢀborabicyclo[3.3.1]nonane (6). The
Grignard reagent prepared from ButCl (5.4 g, 57 mmol) and Mg
(1.4 g, 57.5 mmol) in Et2O (25 mL) was added dropwise to a
solution of compound 4 (6.52 g, 28 mmol) in pentane (25 mL).
The reaction mixture was stirred for 3 h and filtered. The solvent
was distilled off in vacuo and the residue was distilled. Comꢀ
pound 6 was prepared in a yield of 5.07 g (70%), b.p. 127—128 °C
(5•10–2 Torr), nD 1.5348. Found (%): C, 85.03; H, 10.70;
nD 1.5615. Found (%): C, 85.73; H, 9.11; B, 5.15. C15H19B.
20
20
1
B, 4.26. C18H27B. Calculated (%): C, 84.78; H, 10.61; B, 4.10.
1H NMR (CDCl3), δ: 0.79 (s, 9 H, But); 1.02 (dd, 2 H, H(2β),
Calculated (%): C, 85.66; H, 9.05; B, 5.11. H NMR (CDCl3),
δ: 0.64 (s, 3 H, CH3); 1.1, 1.2, 1.25, and 1.31 (all m, 2 H, H(2β),
H(4β)); 1.50, 1.56, 1.61, and 1.68 (all m, 2 H, H(2α), H(4α));
1.68, 1.72, 1.85, and 1.91 (all m, 2 H, Hsyn(9), Hanti(9));
2.15 (dd, 1 H, H(8α)); 2.52, 2.65 (m, 2 H, H(1), H(5));
2.66, 2.75 (m, 1 H, H(8β)); 6.12 (m, 1 H, H(6)); 7.10—7.35
(m, 5 H, Ph).
3ꢀHexyloxyꢀ7αꢀmethylꢀ3ꢀborabicyclo[3.3.1]nonane was preꢀ
pared analogously to compound 15 from 3ꢀmethoxyꢀ7αꢀmeꢀ
thylꢀ3ꢀborabicyclo[3.3.1]nonane (7.78 g, 46.9 mmol) and hexyl
alcohol (4.79 g, 46.9 mmol). The yield was 9.1 g (82%), b.p.
120—123 °C (1.5 Torr). Found (%): C, 76.27; H, 12.38; B, 4.58.
C15H29BO. Calculated (%): C, 76.01; H, 12.12; B, 3.98.
1H NMR (CDCl3), δ: 0.80—1.00 (m, 8 H, H(2β), H(4β), 2 CH3);
1.05—1.45 (m, 9 H, H(6α), H(8α), Hsyn(9), (CH2)4); 1.50—1.70
(m, 3 H, H(2α), H(4α), Hanti(9)); 1.75—2.0 (m, 3 H, H(6β),
H(8β), H(7)); 2.15—2.2 (m, 2 H, H(1), H(5)); 3.75—3.90 (t, 2 H,
H(—O—CH2)). 13C NMR (CDCl3), δ: 13.94 (C(CH2CH3));
22.59 (C(5´)); 24.33 (C(CHCH3)); 25.35 (C(4’); 25.52 (C(7));
27.07 (C(1), C(5), C(2), C(4)); 31.42 (C(3´)); 31.58 (C(2´));
34.09 (C(9)); 65.15 (C(1´)).
3ꢀAllylꢀ7αꢀmethylꢀ3ꢀborabicyclo[3.3.1]nonane (13) was synꢀ
thesized analogously to compound 2 from 3ꢀhexyloxyꢀ7αꢀ
methylꢀ3ꢀborabicyclo[3.3.1]nonane (11.6 g, 39 mmol) and
allylmagnesium bromide prepared from Mg (1.89 g, 77.8 mmol)
and AllBr (4.72 g, 39 mmol) in Et2O. Compound 13 was isolated
in a yield of 7.79 g (84%), b.p. 115—120 °C (1.5 Torr).
Found (%): C, 81.14; H, 11.92; B, 5.28. C12H21B. Calcuꢀ
lated (%): C, 81.84; H, 12.02; B, 6.14. 1H NMR (tolueneꢀd8), δ:
2
3
H(4β), JH(2β),H(2α) = 18.03 Hz, JH(2β),(H1) = 5.61 Hz); 1.23
(br.d, 1 H, Hsyn(9), 2JH
(9) = 12.95 Hz); 1.27 (ddd, 2 H,
(9),H
syn
anti
2
3
H(6α), H(8α), JH(6α),H(6β) = 14.05 Hz, JH(6α),H(5) = 3.52 Hz,
3JH(6α),H(7)
2JH(2
=
9.9 Hz); 1.72 (dd,
= 18.03 Hz); 1.98 (dm, 1 H, Hanti(9)); 2.16 (ddd,
β
2 H, H(2α), H(4α),
α
),H(2 )
2
3
2 H, H(6β), H(8β), JH(6β),H(6α) = 14.05 Hz, JH(6β),H(7)
=
5.5 Hz, 3JH(6β),H(5) = 8.61 Hz); 2.33 (m, 2 H, H(1), H(5)); 2.83
(tt, 1 H, H(7)); 7.13 (t, 1 H, H(pꢀPh), 2J = 7.21 Hz); 7.19 (d,
2 H, H(oꢀPh), 2J = 7.21 Hz); 7.25 (t, 2 H, H(mꢀPh), 2J =
7.61 Hz).
3ꢀMethylaminoꢀ7αꢀphenylꢀ3ꢀborabicyclo[3.3.1]nonane (7).
Gaseous MeNH2 (1.06 g, 34.2 mmol) was introduced into a
solution of compound 3 (1.47 g, 6.3 mmol) in CH2Cl2 (20 mL).
The reaction mixture was stirred for 0.5 h, the solvent was disꢀ
tilled off, and the residue was distilled. Compound 7 was isoꢀ
lated in a yield of 0.74 g (51.7%), b.p. 125—126 °C (1.5 Torr),
m.p. 59—60 °C. Found (%): C, 84.97; H, 10.25; B, 4.78.
C
15H22BN. Calculated (%): C, 84.27; H, 9.98; B, 4.32. 1H NMR
(tolueneꢀd8), δ: 0.71 (br.d, 1 H, H(4α), 2JH(4α),H(4β) = 15.2 Hz);
2
3
0.77 (dd, 1 H, H(2β), JH(2 ),H(2 = 15.62 Hz, JH(2 ),H(1)
=
β
α
β
)
2
6.01 Hz); 0.89 (dd, 1 H, H(4β), JH(4β),H(4α) = 15.22 Hz,
3JH(4β),(H5) = 6.01 Hz); 1.15—1.21 (m, 3 H, H(6α), H(8α),
H(2α)); 1.26 (dm, 1 H, Hsyn(9), 2JH
(dm, 1 H, Hanti(9), 2JH
(9) = 12.8 Hz); 1.89
anti
= 12.81 Hz); 2.11 (m, 2 H,
(9),H
syn
(9),H (9)
anti
H(6β), H(8β)); 2.30 and 2.36 s(ybnoth m, 2 H, H(1), H(5)); 2.61
2
3
(d, 3 H, CH3, J = 6.01 Hz); 2.77 (tt, 1 H, H(7), JH(7),H(6
11.61 Hz, JH(7),H(6β) = 5.21 Hz); 3.75 (br.s, 1 H, (NH));
=
α
)
3