J.-B. Behr, A. Erard, G. Guillerm
FULL PAPER
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Compound 10: [α]2D0 ϭ Ϫ3.7 (c ϭ 0.86, CHCl3). H NMR (CDCl3,
1454, 1101. MS (CI/NH3): m/z (%) ϭ 534 (100) [MHϩ]. HRMS
250 MHz): δ ϭ 7.37Ϫ7.17 (m, 20 H, Ar-H), 5.68 (m, 1 H, 2-H), (CI/NH3): calcd. for C36H40NO3 [MHϩ] 534.3008, found 534.2925.
5.11Ϫ5.06 (m, 2 H, 1a,b-H), 4.63Ϫ4.39 (m, 6 H, OCH2Ph), 4.05
(d, J ϭ 13.0 Hz, 1 H, 7-H), 3.85 (d, 1 H, JAB ϭ 12.5, NCH2Ph),
Synthesis of Diols 13؊16
3.81 (d, J ϭ 5.0 Hz, 1 H, 6-H), 3.73 (d, 1 H, NCH2Ph), 3.70 (dd,
General Procedure: A solution of OsO4 (250 mg OsO4 in 50 mL of
J ϭ 5.0, 5.0 Hz, 1 H, 5-H), 3.58 (dd, J ϭ 9.0, 5.5 Hz, 1 H, 8a-H),
tBuOH and 0.25 mL of tBuOOH, 2.0 mL) was added drop by drop
3.51 (m, 1 H, 8b-H), 3.00 (dd, J ϭ 11.0, 5.5 Hz, 1 H, 4-H), 2.53
to a solution of alkene 11 (1.151 g, 2.16 mmol) and NMO (0.581 g,
(m, 1 H, 3a-H), 2.44 (m, 1 H, 3b-H). 13C NMR (CDCl3,
4.30 mmol) in acetone/water (3.5 mL/1.0 mL), and the mixture was
stirred for 24 h at room temp. Saturated Na2SO3 (20 mL) was then
62.5 MHz): δ ϭ 139.2Ϫ138.6 (Ar-C), 135.3 (C-2), 128.5Ϫ127.2
(Ar-C), 118.0 (C-1), 79.1 (C-5), 78.5 (C-6), 73.9, 73.1, 72.9 (3 ϫ
added, and the solution was extracted twice with EtOAc (2 ϫ
OCH2Ph), 70.9 (C-8), 67.5 (C-7), 57.7 (C-4), 50.9 (NCH2Ph), 33.7
30 mL). The organic layer was washed with water and brine and
˜
(C-3). IR (film): ν ϭ 2863, 1496, 1454, 1071. MS (CI/NH3): m/z
dried (MgSO4). Evaporation of the volatiles gave a crude mixture
of the diols, which were separated by FC (CHCl3/Et2O, 5:2, v/v) to
yield 0.584 g (48%) of 13 and 0.487 g (40%) of 14 as yellow oils. The
same procedure was applied to 12 and yielded, after purification by
FC (Et2O), 0.376 g (25%) of 15 and 0.979 g (65%) of 16 as yellow
oils. Compounds 13؊16 were also obtained by the described pro-
cedure,[19] using the AD-mixtures.
(%) ϭ 552 (100) [MHϩ]. HRMS (CI/NH3): calcd. for C36H42NO4
[MHϩ] 552.3114, found 552.3102.
(2R,3R,4R,5R)-2-Allyl-N-benzyl-3,4-bis(benzyloxy)-5-
[(benzyloxy)methyl]pyrrolidine (11): Cyclisation of
9 (0.251 g,
0.456 mmol) was performed in pyridine (0.5 mL) by stirring over-
night in the presence of methanesulfonyl chloride (0.066 mL,
0.91 mmol). Pyridine was evaporated under reduced pressure, and
the residue was diluted in Et2O, washed with water and dried
(MgSO4). Evaporation of the solvent and purification of the crude
material by FC (Et2O/petroleum ether, 7:3, v/v) gave 11 (207 mg,
Compound 13: [α]2D0 ϭ Ϫ17.7 (c ϭ 2.06, CHCl3). 1H NMR (CDCl3,
500 MHz): δ ϭ 7.40Ϫ7.20 (m, 20 H, Ar-H), 4.58 (d, 1 H, JAB
ϭ
12.0, OCH2Ph), 4.57 (d, 1 H, JAB ϭ 12.0, OCH2Ph), 4.45Ϫ4.38
(m, 4 H, OCH2Ph), 4.10 (m, 3 H, 4-H, 3-H, NCH2Ph), 3.80 (m, 1
H, 2Ј-H), 3.60Ϫ3.50 (m, 4 H, 6a-H, 2-H, 3Јa-H, NCH2Ph),
3.35Ϫ3.25 (m, 3 H, 3Јb-H, 6b-H, 5-H), 1.92 (ddd, 1 H, J ϭ 4.9,
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85%) as a yellow oil. [α]2D0 ϭ Ϫ198.8 (c ϭ 0.86, CHCl3). H NMR
(CDCl3, 250 MHz): δ ϭ 7.30Ϫ7.10 (m, 20 H, Ar-H), 5.78 (m, 1 H,
CH2ϪCHϭCH2), 5.01Ϫ4.96 (m, 2 H, CH2ϪCHϭCH2), 4.53 (d, 1 10.3 Hz, 14.3 Hz, 1Јa-H), 1.68 (d, J ϭ 14.3 Hz, 1 H, 1Јb-H). 13C
H, JAB ϭ 12.0, OCH2Ph), 4.49 (d, 1 H, JAB ϭ 12.0, OCH2Ph), 4.47 NMR (CDCl3, 125 MHz): δ ϭ 138.0Ϫ137.7 (Ar-C), 128.5Ϫ127.1
(d, 1 H, JAB ϭ 12.0, OCH2Ph), 4.45 (d, 1 H, JAB ϭ 12.0, OCH2Ph), (Ar-C), 86.4 (C-3), 83.3 (C-4), 73.2, 71.7 and 71.3 (3 ϫ OCH2Ph),
4.48 (s, 2 H, OCH2Ph), 4.04 (d, 1 H, JAB ϭ 13.8, NCH2Ph), 3.95 69.9 (C-5), 66.7 (C-6), 66.2 (C-3Ј), 66.1 (C-2), 62.8 (C-2Ј), 51.5
(dd, J ϭ 2.1, 3.1 Hz, 1 H, 4-H), 3.85 (dd, J ϭ 2.1, 3.9 Hz, 1 H, 3-
(NCH2Ph), 30.2 (C-1Ј). IR (film): ν
˜ ϭ 3405, 3029, 2863, 1496,
H), 3.69 (d, 1 H, JAB ϭ 13.8, NCH2Ph), 3.60 (dd, J ϭ 5.0, 9.2 Hz, 1454, 1097, 1028. MS (CI/NH3): m/z (%) ϭ 568 (100) [MHϩ].
1 H, 6a-H), 3.55 (dd, J ϭ 6.1 9.2 Hz, 1 H, 6b-H), 3.23 (ddd, 1 H,
HRMS (CI/NH3): calcd. for C36H42NO5 [MHϩ] 568.3063, found
J ϭ 3.1, 5.0 Hz, 6.1 Hz, 5-H), 3.14 (dt, 1 H, J ϭ 2 ϫ 3.9, 8.2 Hz, 568.3045.
2-H), 2.46 (m, 1 H, CH2ϪCHϭCH2), 2.30 (m, 1 H, CH2ϪCHϭ
Compound 14: [α]2D0 ϭ Ϫ21.5 (c ϭ 3.12, CHCl3). 1H NMR (CDCl3,
CH2). 13C NMR (CDCl3, 62.5 MHz): δ ϭ 139.3Ϫ138.2 (Ar-C),
135.2 (CH2-CHϭCH2), 128.2Ϫ126.6 (Ar-C), 116.9 (CH2ϪCHϭ
CH2), 85.8 (C-3), 85.7 (C-4), 73.1, 71.3 and 71.2 (3 ϫ OCH2Ph),
69.4 (C-6), 64.4 (C-5), 64.2 (C-2), 50.9 (NCH2Ph), 32.4
500 MHz): δ ϭ 7.40Ϫ7.15 (m, 20 H, Ar-H), 4.70Ϫ4.40 (m, 6 H,
OCH2Ph), 4.12 (t, J ϭ 2.2 Hz, 1 H, 3-H), 4.01 (dd, J ϭ 2.2, 5.0
Hz, 1 H, 4-H), 3.85 (m, 2 H, 2Ј-H, NCH2Ph), 3.70 (m, 3 H, 6a-H,
2-H, 3Јa-H), 3.55 (m, 2 H, NCH2Ph, 3Јb-H), 3.40 (m, 2 H, 6b-H, 5-
H), 1.92 (m, 1 H, 1Јa-H), 1.53 (m, 1 H, 1Јb-H). 13C NMR (CDCl3,
125 MHz): δ ϭ 138.6Ϫ137.6 (Ar-C), 128.5Ϫ127.0 (Ar-C), 88.8 (C-
3), 84.6 (C-4), 73.0, 71.5 and 71.4 (3 ϫ OCH2Ph), 69.6 (C-5), 66.9
(C-6), 66.6 (C-3Ј), 63.4 (C-2), 63.3 (C-2Ј), 51.7 (NCH2Ph), 33.1 (C-
˜
(CH2ϪCHϭCH2). IR (film): ν ϭ 2860, 1495, 1454, 1098. MS (CI/
NH3): m/z (%) ϭ 534 (55) [MHϩ], 492 (68). HRMS (CI/NH3):
calcd. for C36H40NO3 [MHϩ] 534.3008, found 534.2987.
(2S,3R,4R,5R)-2-Allyl-N-benzyl-3,4-bis(benzyloxy)-5-
[(benzyloxy)methyl]pyrrolidine (12): Cyclisation of 10 (0.578 g,
1.05 mmol) was performed in pyridine (1.0 mL), by stirring over-
night with methanesulfonyl chloride (0.16 mL, 2.1 mmol). Pyridine
was evaporated under reduced pressure, and the residue was diluted
in Et2O, washed with water and dried (MgSO4). Evaporation of
the solvent and purification of the crude material by FC (Et2O/
petroleum ether, 7:3, v/v) gave 14 (365 mg, 65%) as a yellow oil.
˜
1Ј). IR (film): ν ϭ 3384, 3030, 2926, 1496, 1454, 1098, 1028. MS
(CI/NH3): m/z (%) ϭ 568 (100) [MHϩ]. HRMS (CI/NH3): calcd.
for C36H42NO5 [MHϩ] 568.3063, found 568.2988.
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Compound 15: [α]2D0 ϭ 11.7 (c ϭ 0.36, CHCl3). H NMR (CDCl3,
500 MHz): δ ϭ 7.40Ϫ7.15 (m, 20 H, Ar-H), 4.65, 4.62, 4.51, 4.40,
4.32 and 4.28 (6d, 6 H, JAB ϭ 12.0, OCH2Ph), 4.11 (dd, 1 H, J ϭ
2 ϫ 4.7, 4-H), 4.02 (dd, J ϭ 4.7, 5.0 Hz, 1 H, 3-H), 4.00 (d, 1 H,
JAB ϭ 13.0, NCH2Ph), 3.70 (d, 1 H, JAB ϭ 13.0, NCH2Ph), 3.63
(m, 1 H, 2Ј-H), 3.50 (dd, J ϭ 3.7, 10.1 Hz, 1 H, 3Јa-H), 3.40 (m,
1 H, 2-H), 3.35 (dd, J ϭ 6.0, 10.1 Hz, 1 H, 3Јb-H), 3.18 (m, 2 H,
6a,b-H), 3.07 (m, 1 H, 5-H), 1.70 (t, J ϭ 6.8 Hz, 2 H, 1Јa,b-H).
1
[α]2D0 ϭ 26.5 (c ϭ 1.32, CHCl3). H NMR (C6D6, 250 MHz): δ ϭ
7.40Ϫ7.10 (m, 20 H, Ar-H), 5.80 (m, 1 H, CH2ϪCHϭCH2),
5.11Ϫ5.00 (m, 2 H, CH2ϪCHϭCH2), 4.58, 4.49, 4.38, 4.21, 4.18
and 4.11 (6d, 6 H, JAB ϭ 12.0, 6 ϫ OCH2Ph), 4.13 (t, J ϭ 1.3 Hz,
1 H, 4-H), 3.91 (d, 1 H, JAB ϭ 13.0, NCH2Ph), 3.89 (ddd, 1 H,
J ϭ 0.8, 1.3 Hz , 4.6 Hz, 3-H), 3.63 (d, 1 H, JAB ϭ 13.0, NCH2Ph),
3.51 (t, J ϭ 9.2 Hz, 1 H, 6a-H), 3.33 (dddd, 1 H, J ϭ 0.8, 1.3, 4.7
Hz, 9.2 Hz, 5-H), 3.25 (dt, 1 H, J ϭ 2 ϫ 4.6, 9.2 Hz, 2-H), 3.20
(dd, J ϭ 4.7, 9.2 Hz, 1 H , 6b-H), 2.70 (m, 1 H, CH2ϪCHϭCH2),
2.35 (m, 1 H, CH2ϪCHϭCH2). 13C NMR (CDCl3, 62.5 MHz):
δ ϭ 139.3Ϫ138.2 (Ar-C), 136.1 (CH2-CHϭCH2), 129.3Ϫ126.9 (Ar-
C), 116.3 (CH2ϪCHϭCH2), 82.5 (C-3), 82.3 (C-4), 72.9, 72.0 and
13C NMR (CDCl3, 125 MHz):
δ ϭ 138.1Ϫ137.5 (Ar-C),
128.5Ϫ127.5 (Ar-C), 82.8 (C-3), 82.7 (C-4), 73.0, 72.0 and 71.9 (3
ϫ OCH2Ph), 70.4 (C-5), 67.2 (C-6), 66.7 (C-2), 65.8 (C-3Ј), 63.5
˜
(C-2Ј), 61.1 (NCH2Ph), 31.2 (C-1Ј). IR (film): ν ϭ 3045, 3029,
2863, 1454, 1072, 1028. MS (CI/NH3): m/z (%) ϭ 568 (100) [MHϩ].
HRMS (CI/NH3): calcd. for C36H42NO5 [MHϩ] 568.3063, found
568.3045.
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71.7 (3 ϫ OCH2Ph), 70.6 (C-6), 69.1 (C-5), 66.6 (C-2), 58.4 Compound 16: [α]2D0 ϭ 11.6 (c ϭ 0.50, CHCl3). H NMR (CDCl3,
˜
(NCH2Ph), 33.0 (CH2ϪCHϭCH2). IR (film): ν ϭ 2861, 1496, 500 MHz): δ ϭ 7.38Ϫ7.20 (m, 20 H, Ar-H), 4.60, 4.58, 4.50, 4.41,
1260 Eur. J. Org. Chem. 2002, 1256Ϫ1262