F. Hammerschmidt, A. Hanninger, B. Peric, H. Völlenkle, A. Werner
FULL PAPER
were added. The organic phase was separated and the aqueous
MHz, CDCl3): δ ϭ 1.18, 1.23 and 1.26 (3 ϫ d, J ϭ 6.9 Hz, each 6
phase was extracted with petroleum ether (20 ml). The combined H, Me2CH), 1.87 (m, 1 H, CH2), 2.01 (m, 1 H, CH2), 2.11 (m, 1
organic layers were washed with water and a saturated solution of
NaHCO3, dried (Na2SO4), and concentrated in vacuo. The residue
was purified by flash chromatography [for deuterated compounds
with eluents as used for 4 or 9, respectively; for stannanes with PE/
diethyl ether (40:1), for Rf see respective compounds].
H, CH2), 2.22 (m, 1 H, CH2), 2.81 (2 overlapping m, 3 H, 4-H,
Me2CH), 2.91 (sept, J ϭ 6.9 Hz, 2 H, Me2CH), 6.31 (t, J ϭ 3.9
Hz, 1 H, CHO), 6.98 (s, 2 H, Harom), 7.11 (m, 1 H, Harom), 7.20
(m, 2 H, Harom), 7.41 (m, 1 H, Harom). Ϫ 13C NMR (100.6 MHz,
CDCl3): δ ϭ 18.53 (CH2), 23.92, 24.08 and 24.16 (each 2 C,
Me2CH), 28.88 (CH2), 29.06 (CH2), 31.30 (2 C, Me2CH), 34.39
(Me2CH), 70.78 (CHO), 120.74 (2 C, HCarom), 125.90, 128.19,
129.04 and 129.89 (4 C, HCarom), 130.60, 134.06, 137.99, 144.61 (2
C) and 149.95 (Carom), 170.42 (CϭO). Ϫ C26H34O2 (378.56): calcd.
C 82.49, H 9.05; found C 82.75, H 9.31.
Lithiodestannylation of Stannanes 6, 11a and 11b Followed by Ad-
dition of MeOD (General Procedure B): A stirred solution of stan-
nane (usually 0.2Ϫ0.5 mmol), 3 equiv. of dry TMEDA in dry hex-
ane (1 ml for each 0.1 mmol) was cooled under argon to Ϫ78°C.
3 equiv. of sBuLi (1.3 solution in cyclohexane, not titrated; some-
times nBuLi was used instead of sBuLi) was added dropwise. After
5 min, MeOD (0.25 ml, in 1 ml of dry hexane) was added. Stirring
was continued for 30 min. The cooling bath was removed. Petro-
leum ether (20 ml) and 2 HCl (10 ml) were added. The organic
phase was separated and the aqueous phase was extracted with
petroleum ether (20 ml). The combined organic layers were washed
with water and a saturated solution of NaHCO3, dried (Na2SO4),
and concentrated in vacuo. The residue was purified by flash chro-
matography with the eluents used for the nondeuterated com-
pounds. The individual reactions are described after the respect-
ive stannanes.
(S)-(؉)-(1-Trimethylstannyl-1-indanyl) 2,4,6-Triisopropylbenzoate
[(S)-(؉)-6a]: Ester (R)-(ϩ)-4a (0.365 g, 1 mmol) was stannylated
according to General Procedure A. The product was purified by
flash chromatography [PE/Et2O (40:1); for TLC: PE/Et2O (20:1),
Rf ϭ 0.64) to give 0.232 g (44%) of stannane (S)-(ϩ)-6a as a viscous
oil which eventually crystallized, m.p. 50Ϫ60°C, [α]D20ϭ ϩ2.83
(c ϭ 1.8, CHCl3). Ϫ IR (Si): ν˜ ϭ 2962 cmϪ1, 1699, 1607, 1461,
1
1255, 1138, 1080. Ϫ H NMR (400 MHz, CDCl3): δ ϭ 0.08 [s, 9
H, SnMe3; J(117/119Sn) ϭ 51.2, 53.2 Hz], 1.21 (d, J ϭ 6.9 Hz, 12
H, Me2CH), 1.24 (d, J ϭ 6.4 Hz, 6 H, Me2CH), 2.26 [dt, J ϭ 8.6,
12.2 Hz, 1 H, 2-Ha; J(117/119Sn) ϭ 58.0, 60.1 Hz], 2.71 (dt, J ϭ 8.6,
15.3 Hz, 1 H, 3-Hb), 2.85 (m, 2 H, Me2CH, 2-Hb), 2.96 (sept, J ϭ
6.9 Hz, 2 H, Me2CH), 3.06 (ddd, J ϭ 2.5, 8.6, 15.3 Hz, 1 H, 3-
Hb), 6.97 (s, 2 H, Harom), 7.17 (m, 4 H, Harom). Ϫ 13C NMR (100.6
MHz, CDCl3): δ ϭ Ϫ7.36 [Me3Sn; J(117/119Sn) ϭ 330.4, 338.0 Hz],
23.91, 24.24 and 24.28 (each 2 C, Me2CH), 30.46 (CH2), 31.16 (2
C, Me2CH), 34.36 (Me2CH), 38.40 [SnCCH2; J(117/119Sn) ϭ 20.0
Hz], 87.74 (SnCO), 120.80 (2 C, CHarom), 123.18, 124.66 126.73
(±)- and (R)-(؉)-(1-Indanyl) 2,4,6-Triisopropylbenzoate [(±)- and
(R)-(؉)-4a]: Diethyl azodicarboxylate (1.045 g 0.94 ml, 6 mmol)
was added dropwise to a stirred and cooled (ice/water) mixture of
(±)-1-indanol (0.671 g, 5 mmol), triphenylphosphane (1.57 g, 6
mmol), and 2,4,6-triisopropylbenzoic acid (1.24 g, 5 mmol) in dry
toluene (20 ml) under argon. Stirring was continued for 1 hr at 0°C
and 4 h at ambient temperature. Then the toluene was removed in
vacuo and the residue was taken up in petroleum ether. After 2 h,
the crystalline material (Ph3PO and hydrazo ester) was filtered off.
The mother liquor was concentrated in vacuo and purified twice
by flash chromatography [PE/Et2O (40:1); Rf ϭ 0.42 with PE/Et2O
(20:1)] to yield (±)-4a as a viscous, colorless oil (1.17 g, 64%). Ϫ
(S)-(ϩ)-2a (0.671 g, 5 mmol) was esterified similarly to give (R)-
(ϩ)-4a {1.39 g (76%); [α]D20ϭ ϩ1.91 (c ϭ 5.71, CHCl3)}. Ϫ IR
(Si): ν˜ ϭ 2962 cmϪ1, 1723, 1461, 1249, 1136, 1075. Ϫ 1H NMR
(400 MHz, CDCl3): δ ϭ 1.14 (d, J ϭ 6.9 Hz, 6 H, Me2CH), 1.20
(d, J ϭ 6.9 Hz, 12 H, Me2CH), 2.23 (dddd, J ϭ 3.0, 3.9, 7.4, 14.3
Hz, 1 H, 2-Hb), 2.55 (ddt, J ϭ 7.4, 8.4, 14.3 Hz, 1 H, 2-Ha), 2.84
(sept, J ϭ 6.9 Hz, 3 H, Me2CH), 2.90 (ddd, J ϭ 3.9, 8.4, 16.0 Hz,
1 H, 3-Ha), 3.11 (dt, J ϭ 7.4, 16.0 Hz, 1 H, 3-Hb), 6.46 (dd, J ϭ
3.0, 7.4 Hz, 1 H, 1-H), 6.95 (s, 2 H, Harom), 7.24 (m, 3 H, Harom),
7.50 (d, J ϭ 7.4 Hz, 1 H, Harom). Ϫ 13C NMR (100.6 MHz,
CDCl3): δ ϭ 23.93 (2 C, Me2CH), 24.04 (4 C, Me2CH), 30.35
(CH2), 31.26 (2 C, Me2CH), 32.24 (PhCH2), 34.41 (Me2CH), 79.02
(CHO), 120.75 (2 C, HCarom), 124.78, 125.76, 126.58 and 129.04 (4
C, HCarom), 130.47 and 140.81 (2 C, Carom), 144.66 (2 C, iPrCarom),
150.04 (OCCarom), 170.72 (CϭO). Ϫ C25H32O2 (364.53): calcd. C
82.37, H 8.84; found C 82.74, H 8.89.
and 126.79 (4 C, HCarom), 130.03 (Carom), 140.56 [Carom
;
J(117/119Sn) ϭ 20.6 Hz], 145.02, 146.56 (2 C) and 150.07 (Carom),
172.00 (CϭO). Ϫ C28H40O2Sn (527.23): calcd. C 63.77, H 7.65;
found C 64.06, H 7.95. Ϫ Stannane (ϩ)-6a (0.092 g, 0.175 mmol)
was transformed into 0.037 g (58%) of deutero-(R)-(ϩ)-4a {[α]D20ϭ
ϩ0.12 (c ϭ 0.95, CHCl3); ee 5% by HPLC} according to General
Procedure B using sBuLi.
(S)-(؉)-(1,2,3,4-Tetrahydro-1-trimethylstannyl-1-naphthyl)
2,4,6-
Triisopropylbenzoate [(S)-(؉)-6b]: Ester (S)-(Ϫ)-4b (0.757 g, 2
mmol) was stannylated in hexane (15 ml) according to General
Procedure A. The residue was purified by flash chromatography
[PE/Et2O (40:1), Rf ϭ 0.51] to give crystalline (S)-(ϩ)-6b (1.083 g,
74%); [α]D20ϭ ϩ9.16 (c ϭ 36.1, CHCl3). Ϫ IR (Si): ν˜ ϭ 2962 cmϪ1
,
1
1698, 1461, 1288, 1257. Ϫ H NMR (400 MHz, CDCl3): δ ϭ 0.08
[s, 9 H, SnMe3; J(117/119Sn) ϭ 49.7, 51.7 Hz], 1.22, 1.25 and 1.29
(3d, J ϭ 6.9 Hz, each 6 H, Me2CH), 1.81 and 1.98 (2m, each 1 H,
3-H), 2.19 [ddd, 1 H, J ϭ 3.0, 11.3, 12.8 Hz, 2-Ha; J(117/119Sn) ϭ
69.0, 71.4 Hz], 2.62 [ddd, J ϭ 3.0, 6.6, 12.8 Hz, 1 H, 2-Hb;
J(117/119Sn) ϭ 30.0, 33.3 Hz], 2.74 (B part of ABXY system, dt,
J ϭ 4.9, 16.7 Hz, 4-Ha), 2.87 (A part of ABXY system overlapping
with sept, J ϭ 6.9 Hz, 2 H, 4-Hb, Me2CH), 3.03 (sept, J ϭ 6.9 Hz,
2 H, Me2CH), 6.99 (s, 2 H, Harom), 7.05 (m, 2 H, Harom), 7.12 (m,
1 H, Harom), 7.20 (m, 1 H, Harom). Ϫ 13C NMR (100.6 MHz,
(S)-(؊)- and (R)-(؉)-(1,2,3,4-Tetrahydro-1-naphthyl) 2,4,6-Triisop-
ropylbenzoate [(S)-(؊)- and (R)-(؉)-4b]: (R)-(Ϫ)-1-Tetralol (0.741 CDCl3): δ ϭ Ϫ6.67 [Me3Sn; J(117/119Sn) ϭ 325.8, 340.3 Hz], 20.27
g, 5 mmol) was esterified by the procedure used for the preparation
of (±)-4a. Flash chromatography [PE/Et2O (40:1); Rf ϭ 0.45 with
PE/Et2O (20:1)] gave ester (S)-(Ϫ)-4b (1.617 g, 85%) as viscous oil,
which contained possibly some anhydride and gradually solidified;
[CH2; J(117/119Sn) ϭ 13.0 Hz], 23.91 and 23.93 (each 1 C, Me2CH),
24.23 and 24.44 (each 2 C, Me2CH), 29.22 (CH2), 31.24 (2 C,
Me2CH), 33.60 [CH2; J(117/119Sn) ϭ 10.6 Hz], 34.36 (Me2CH),
82.73 (OCSn), 120.81 (2 C, HCarom), 125.77 [HCarom; J(117/119Sn) ϭ
m.p. 55Ϫ65°C; [α]D20ϭ Ϫ3.56 (c ϭ 5.2, CHCl3), [α]43620ϭ Ϫ10.06 9.9 Hz], 126.06 [HCarom; J(117/119Sn) ϭ 8.4 Hz], 126.55 [HCarom
;
(c ϭ 5.2, CHCl3). Ϫ (S)-(ϩ)-1-Tetralol (0.741 g, 5 mmol) was es-
J(117/119Sn) ϭ 19.1 Hz], 129.03 (HCarom), 130.17 (Carom), 135.03
[Carom; J(117/119Sn) ϭ 9.8 Hz], 140.44 (Carom), 144.89 (2 Carom),
terified similarly to give (R)-(ϩ)-4b (1.31 g, 69%); [α]D20ϭ ϩ3.84
(c ϭ 4.3, CHCl3), [α]43620ϭ ϩ11.09 c ϭ 4.3, CHCl3). Ϫ IR (Si): 150.01 (Carom), 172.07 (CϭO). Ϫ C29H42O2Sn (541.34): calcd. C
ν˜ ϭ 2961 cmϪ1, 1721, 1460, 1250, 1075, 1058. Ϫ 1H NMR (400 64.34, H 7.84; found C 64.40, H 7.99. Ϫ Stannane (ϩ)-6b (0.391
3516
Eur. J. Org. Chem. 1999, 3511Ϫ3518