實驗步驟及光譜資料

第五章實驗部份

5.2 實驗步驟及光譜資料

1,1’-Binaphthalene-2-20-diol rac-1.

⁵³

OH OH

rac-1 83%

OH FeCl₃

H₂O, 50-60 ^oC, 2 h

FeCl

₃

‧6H

2

O (19.44 g, 71.9 mmol) was dissolved in water (50mL) and 2-naphthol (5.18 g, 35.9 mmol) was added to the solution at 50-60

^o

C for 1.5-2 h. The solvent was removed by suction filtration, and the precipitate washed with water. Then, residue was dissolved in CHCl

₃

(100 mL) and partitioned between water and CHCl

3

. The organic layer was dried over anhydrous MgSO

4

. The solvent was removed under reduced pressure and the residue was recrystallized from acetone/toluene.

The yield is 83% as a yellow solid.

¹

H NMR (CDCl

₃

, 300MHz) δ

_H

7.99 (d, J = 8.7 Hz, 2H, ArH), 7.90 (d, J = 7.3 Hz, 2H, ArH), 7.40-7.26 (m, 6H), 7.15 (d, J = 8.7 Hz, 2H, ArH), 5.03 (s, 2H, ArOH).

¹³

C-NMR (75.4 MHz, CDCl

3

) δ 152.7, 133.4, 131.4, 129.4, 128.4, 127.5, 124.2, 124.0, 117.7, 110.8; mp 205-208

^o

C; FAB-MS: m/z (%)

General Procedure for the Synthesis of 36a and 36b.

^54a

I O nOH Cl O nOH

NaI, acetone reflux, 18 h

36a n = 1 97%

36b n = 2 96%

35a n = 1 97%

35b n = 2 96%

126

35a or 35b (35a: 7.0 g, 56.2 mmol; 35b: 7.0 g, 41.5 mmol) and NaI (35 g, 0.23 mol; 35 g, 0.23 mol) were refluxed vigorously overnight in acetone (50 mL). After cooling, the slurry was taken up in the minimum amount of water and extracted with Et

₂

O (50 mL). The organic layers were dried (MgSO

4

), filtered, and evaporated to dryness to give the compound 36a or 36b (36a: 11.8 g, 54.5 mmol, 97%; 36b: 10.5 g, 39.8 mmol, 96%) as brown oil which was used in the next step without further purification.

Data for 2-(2-Iodoethoxy)ethanol (36a):

¹

H NMR (CDCl

3

, 300MHz) δ

H

3.73-3.69 (m, 4 H, OCH

2

O), 3.58-3.55 (m, 2 H, OCH

2

OH), 3.23 (t, 2 H, ICH

₂

O), 2.98 (br, 1 H, OCH

₂

OH);

¹³

C-NMR (75.4 MHz, CDCl

3

) δ 71.8 (CH

₂

), 71.3 (CH

2

), 61.5 (CH

2

), 3.2 (CH

2

Data for 2-[2-(2-Iodoethoxy)ethoxy]ethanol (36b):

¹

H NMR (CDCl

₃

, 300MHz) δ

_H

7.94 (d, J = 9.0 Hz, 2H, ArH), 7.86 (d, J = 8.4 Hz, 2H, ArH), 7.42 (d, J = 9.0 Hz, 2 H, ArH), 7.34-7.19 (m, 4H), 7.12 (d, J = 8.4 Hz, 2H, ArH), 4.16-3.09 (m, 26H, );

¹³

C-NMR (75.4 MHz, CDCl

3

) δ 72.4 (CH

2

), 71.9 (CH

₂

), 70.0 (CH

₂

), 69.9 (CH

₂

), 61.4 (CH

₂

), 3.9 (CH

₂

General Procedure for the Synthesis of (S)-(-)-37a, (S)-(-)-37b, and

rac-37b. ^54a

OH OH

O O

O OH

OH n

n K₂CO₃, acetone

rt. 72 h

(S)-(-)-37a n = 1 80%

(S)-(-)-37b n = 2 85%

rac-37b n = 2, 90%

I O nOH

rac-1 (S)-(-)-1

36a n = 1

36b n = 2

127

A mixture of rac-1 or (S)-(-)-34 (rac-34: 1.00 g, 3.5 mmol;

(S)-(-)-34: 1.00 g, 3.5 mmol), 36a or 36b (36a: 1.8 g, 8.4 mmol; 36b: 2.2 g, 8.4 mmol) and K

2

3

(4.62 g, 35.0 mmol) in acetone (10 mL) was stirred under N

₂

system at room temperature for three days. After the addition of 10 mL of acetone, the solid was filtered off and washed with acetone (10 mL). The organic phase was evaporated to dryness and the crude material was purified over silica gel column elution with hexane/acetone (rac-37b : v/v = 1/2; (S)-(-)-37a: v/v = 1/1; (S)-(-)-37b:

v/v = 1/2) to give the compound rac-37b or (S)-(-)-37a or (S)-(-)-37b (rac-37b: 1.73 g, 90%; (S)-(-)-37a: 1.15 g, 80%; (S)-(-)-37b: 1.63 g, 85%) as a yellow oil.

Data for (S)-(-)-37a:

¹

H NMR (CDCl

3

, 300MHz, Figure ) δ

_H

7.99 (d, J = 9.0 Hz, 2 H, ArH), 7.90 (d, J = 8.4 Hz, 2H, ArH), 7.45 (d, J = 9.0 Hz, 2H, ArH), 7.40-7.23 (m, 4H, ArH), 7.17 (d, J = 8.4 Hz, 2H, ArH), 4.33-4.16 (m, 2H, OCH

₂

O), 4.06-4.00 (m, 2H, OCH

₂

O), 3.57-3.38 (m, 8H, OCH

2

O), 3.28-3.16 (m, 4H, OCH

2

O), 2.47 (br s, 2H, CH

2

OH);

13

C-NMR (75.4 MHz, CDCl

3

) δ 154.0 (C

q

), 133.8 (C

q

), 129.2 (C

q

), 129.1 (CH), 127.7 (CH), 126.1 (CH), 125.1 (CH), 123.6 (CH), 120.3 (C

q

), 115.7 (CH), 72.2 (CH

2

), 69.5 (CH

2

), 69.2 (CH

2

) , 61.2 (CH

2

); [α]

D 25

= -21.6 (c = 0.025, CHCl

₃

). FAB-MS: m/z (%) 486 (M + Na

⁺

, 9), 463 (M

⁺

, 100), 239 (45).

Data for (S)-(-)-37b:

¹

H NMR (CDCl

3

, 300MHz, Figure ) δ

H

7.94 (d, J = 9.0 Hz, 2H, ArH), 7.86 (d, J = 8.4 Hz, 2 H, ArH), 7.42 (d, J = 9.0 Hz, 2H, ArH), 7.34-7.19 (m, 4H), 7.12 (d, J = 8.4 Hz, 2H, ArH), 4.17-3.10 (m, 26H, ), (br s, 2H, OH);

¹³

C-NMR (75.4 MHz, CDCl

3

) δ 154.1 (C

q

), 134.0 (C

_q

), 129.3 (C

_q

), 129.2 (CH), 127.7 (CH), 126.2 (CH), 125.3 (CH), 120.4

128

(Cq), 115.5 (CH), 72.3 (CH

2

), 70.4 (CH

2

), 70.1 (CH

2

) , 69.8 (CH

2

), 69.5 (CH

2

), 61.5 (CH

2

); [α]

D

25

= -39.7 (c = 0.030, CHCl

3

). FAB-MS: m/z (%) 573 (M + Na

⁺

, 11), 551 (M

⁺

, 100).

General Procedure for the Synthesis of (S)-(-)-38a, (S)-(-)-38b.

⁵⁴

TsCl TEA, DMAP, DCM

rt. 48 h

O O

O OTs OTs n

(S)-(-)-38a n = 1 76%

(S)-(-)-38b n = 2 77%

rac-38b n = 2 58%

O O

O OH

OH n

(S)-(-)-37a n = 1 (S)-(-)-37b n = 2 rac-37b n = 2

A mixture of diol (S)-(-)-37a or (S)-(-)-37b or rac-37b ((S)-(-)-37a:

1.10 g, 2.40 mmol; (S)-(-)-37b: 0.83 g, 1.50 mmol; rac-37b: 0.60 g, 1.09 mmol), p-toluenesulfonyl chloride (1.80 g, 9.4 mmol; 1.15 g, 6.0 mmol;

0.83 g, 4.86 mmol), Et

3

N (1.32 mL, 9.40 mmol; 0.61 mg, 6.00 mmol;

0.83 g, 4.36 mmol) and a catalytic amount of 4-(dimethylamino) pyridine were dissolved in CH

2

(55 mL), and this solution was stirred under N

2

system at room temperature for two days. The crude material was purified over silica gel column elutiong with hexane/acetone ((S)-(-)-38a: v/v = 5/1; (S)-(-)-38b: v/v = 3/1; rac-38b : v/v = 3/1) to give the compound (S)-(-)-38a or (S)-(-)-38b or rac-38b ((S)-(-)-38a: 1.39 g, 76%;

(S)-(-)-38b: 0.71 g, 77%; rac-38b: 0.54 g, 58%) as a yellow oil.

Data for (S)-(-)-38a:

¹

H NMR (CDCl

₃

, 300MHz) δ

_H

7.90 (d, J = 9.0 Hz, 2H, ArH), 7.81 (d, J = 8.0 Hz, 2H, ArH), 7.72-7.69 (m, J = 4H, ArH), 7.34 (d, J = 9.0 Hz, 2H, ArH), 7.32-7.16 (m, 6H, ArH), 7.21-7.10 (m, 4H, ArH), 4.07-3.95 (m, 4H, OCH

2

O), 3.67-3.59 (m, 4H, OCH

2

O), 3.37 (t, J = 4.5 Hz, 4H, OCH

₂

O), 3.03-2.88 (m, 4H, OCH

₂

O),

129

2.42 (s, 6H, ArCH

3

);

¹³

C-NMR (75.4 MHz, CDCl

3

, Figure ) δ 153.9 (C

q

), 144.6 (C

q

), 133.8 (C

q

), 132.9 (C

q

), 129.6 (CH), 129.2 (CH), 129.1 (C

q

), 127.8 (CH), 127.7 (CH), 126.2 (CH), 125.2 (CH), 123.6 (CH), 120.1 (C

q

), 115.1 (CH), 69.8 (CH

₂

), 69.3 (CH

₂

), 69.1 (CH

₂

), 68.3 (CH

₂

), 21.5 (CH

₃

);

[α]

D

25

= -32.2 (c = 0.023, CHCl

3

). FAB-MS: m/z (%) 771 (M

⁺

, 100), 308 (31).

Data for (S)-(-)-38b:

¹

H NMR (CDCl

₃

, 300MHz, Figure ) δ

_H

7.91 (d, J = 9 Hz, 2H, ArH), 7.83 (d, J = 8.1 Hz, 2H, ArH), 7.75 (d, J = 8.1 Hz, 2H, ArH), 7.39 (d, J = 9.0 Hz, 2H, ArH) 7.30 (d, J = 8.1 Hz, 2 H, ArH), 7.18-7.10 (m, 10H,ArH), 4.08-4.01 (m, 8H), 3.46-3.42 (m, 8H), 3.12-2.99 (m, 8H) 2.39 (s, 6H, ArCH

₃

);

¹³

C-NMR (75.4 MHz, CDCl

₃

, Figure ) δ 154.1 (C

q

), 144.7 (C

q

), 133.9 (C

q

), 132.8 (C

q

), 129.7 (CH), 129.2 (C

q

), 129.2 (CH), 127.8 (CH), 127.7 (CH), 126.2 (CH), 125.3 (CH), 123.6 (CH), 120.3 (C

q

), 115.4 (CH), 70.4 (CH

2

), 70.3 (CH

2

), 69.8 (CH

2

), 69.5 (CH

₂

), 69.1 (CH

₂

), 68.3 (CH

₂

), 21.5 (CH

₃

); [α]

_D ²⁵

= -37.9 (c = 0.025, CHCl

3

). FAB-MS: m/z (%) 882 (M + Na

⁺

, 3), 859 (M

⁺

, 100).

25,26-bis[(2-benzloxy]-27,28-dihydroxy-p-tertbutylcalix[4]arene 39.

^56b

O OH HO O

39 42%

OHOH HO OH

20

NaH, CH₃CN, rt. 2 h + O O O O

40 17%

A mixture of tert-butylcalix[4]arene 20 (2.0 g, 3.1mmol) and sodium hydride (0.62 g, 15.4 mmol) was stirred at room temperature for 1 h.

Then, benzylbromide (1.16 g 6.8 mmol) was added to the solution at

130

room temperature for 1.2 h. Then a small amount of 10% HCl was added to quench the reaction. The solvent was removed under reduced pressure, and the residue was partitioned between water and CH

2

. The organic layer was dried over anhydrous MgSO

₄

. The crude material was purified over silica gel column elutiong with hexane/ CH

2

(v/v = 3/1) to give

rac-41a and rac-41b.

O OH HO

131

A mixture of compound 39 (0.30 g, 0.3 mmol; 0.80 g, 0.96 mmol) and potassium tert-butyloxide (0.10 mg, 0.9 mmol; 0.27 g, 2.4 mmol) in toluene (120 mL; 300 mL) was stirred under N

2

system at 70

^o

C for 0.5 h.

Then the compound (S)-(-)-38b or rac-38b ((S)-(-)-38b: 0.35 mg, 0.4 mmol; rac-12b: 0.96 g, 1.1 mmol) was added to the solution for 48 h. The solvent was removed under reduced pressure and the residue was partitioned between water and CH

₂

. The organic layer was dried over anhydrous MgSO

4

. The crude material was purified over silica gel column elutiong with hexane/ethyl acetate (v/v = 4/1) to give the compound (S)-(-)-41a or rac-41a ((S)-(-)-41b: 0.13 g, 26%; rac-41b: 0.15 g, 30%) and the compound (S)-(-)-41b or rac-41b ((S)-(-)-41b: 0.18 g, 38%; rac-41b: 0.16 g, 32%) as a white solid.

Data for (S)-(-)-41a: R

_f

= 0.35 (silica, hexane/ethyl acetate = 4/1)

¹

H NMR (CDCl

3

, 300MHz) δ

_H

7.91 (d, J = 9.0 Hz, 1H, ArH), 7.84 (d, J = 8.2 Hz, 1H, ArH),7.79 (d, J = 8.2 Hz, 1H, ArH), 7.76 (d, J = 9.0 Hz, 1H, ArH), 7.42 (d, J = 9.0 Hz, 1H, ArH), 7.36-6.61 (m, 25H, ArH), 4.46-4.33 (m, 5H, ArCh

₂

Ar, ArOCH

₂

Ph), 4.10-3.68 (m, 5H, OCH

₂

O, ArCh

₂

Ar), 3.57-2.95 (m, 20H, OCH

2

O), 2.59-2.46 (m, 2H, OCH

2

Ar), 1.40-1.26 (m, 18H, CH

3

), 1.21-1.15 (m, 18H, CH

3

);

¹³

C-NMR (75.4 MHz, CDCl

3

) δ 154.5 (C

q

), 154.4 (C

q

), 154.2 (C

q

), 154.1 (C

q

), 153.3 (C

q

), 153.1 (C

_q

), 144.5 (C

_q

), 144.5 (C

_q

), 144.4 (C

_q

), 138.4 (C

_q

), 138.3 (C

_q

), 134.6 (C

_q

), 134.4 (C

_q

), 134.0 (C

_q

), 133.9 (C

_q

), 133.8 (C

_q

), 132.5 (C

_q

), 132.4 (C

_q

), 132.2 (C

q

), 132.1 (C

q

), 129.4 (CH), 129.3 (CH), 129.2 (CH), 129.0 (CH), 127.7 (CH), 127.1 (CH), 126.5 (CH), 126.4 (CH), 126.1 (CH), 126.0 (CH), 125.5 (CH), 125.4 (CH), 125.3 (CH), 125.2 (CH), 123.6 (CH), 123.4 (CH), 120.6 (C

_q

), 120.3 (C

_q

), 116.1 (CH), 116.0 (CH), 74.2 (CH

₂

), 74.1 (CH

2

), 70.7 (CH

2

), 70.5 (CH

2

), 70.4 (CH

2

), 70.2 (CH

2

), 69.7 (CH

2

132

69.6 (CH

2

), 69.5 (CH

2

), 68.6 (CH

2

), 68.5 (CH

2

), 38.9 (CH

2

), 34.1 (C

q

), 34.0 (C

q

), 33.9 (C

q

), 33.8 (C

q

), 31.7 (CH

3

), 31.5 (CH

3

), 31.7 (CH

2

), 31.5 (CH

2

), 31.4 (CH

2

); mp 112-114

^o

C; [α]

D 25

= -38.9 (c = 0.013, CHCl

3

FAB-MS: m/z (%) 1366 (M + Na

⁺

, 3), 611 (66), 313 (100).

Data for rac-41a: R

f

=0.35 (silica, hexane/ethyl acetate = 4/1) mp 110-113

^o

¹

H NMR (CDCl

₃

, 300MHz) δ

_H

7.92 (d, J = 9.0 Hz, 1H, ArH), 7.85 (d, J = 8.0 Hz, 1H, ArH),7.79 (d, J = 8.0 Hz, 1H, ArH), 7.78 (d, J = 9.0 Hz, 1H, ArH), 7.42 (d, J = 9.0 Hz, 1H, ArH), 7.336-6.62 (m, 25H, ArH), 4.47-4.34 (m, 6H, ArCh

2

Ar, ArOCH

2

Ph), 4.34-3.95 (m, 29H, OCH

2

O, ArCh

2

Ar ), 2.63-2.45 (m, 2H, OCH

2

Ar), 1.40-1.26 (m, 18H, CH

₃

), 1.21-1.15 (m, 18H, CH

₃

Data for (S)-(-)-41b: R

_f

= 0.23 (silica, hexane/ethyl acetate = 4/1)

¹

H NMR (CDCl

₃

, 300MHz) δ

_H

7.89-7.81 (m, 4 H, ArH), 7.42-6.72 (m, 26H, ArH), 4.93-4.83 (m, 4H, ArOCH

2

Ar), 4.47 (d, 1H, J = 12.6 Hz, ArCH

2

Ar), 4.28 (d, 1H, J = 12.5 Hz, ArCH

2

Ar) 4.26 (d, 1H, J = 12.5 Hz, ArCH

2

Ar), 4.17-3.31 (m, 24H, OCH

2

O), 3.09 (d, 1H, J = 12.6 Hz, ArCH

₂

Ar), 3.01 (d, 1H, J = 12.6 Hz, ArCH

₂

Ar), 2.99 (d, 1H, J = 12.6 Hz, ArCH

2

Ar), 2.89 (d, 1H, J = 12.6 Hz, ArCH

2

Ar), 1.09-1.06 (m, 36H, CH

3

);

13

C-NMR (75.4 MHz, CDCl

3

) δ 154.4 (C

_q

), 153.2 (C

q

), 153.1 (C

q

), 157.0 (C

q

), 152.6 (C

q

), 144.6 (C

q

), 144.5 (C

q

), 138.3 (C

q

), 134.0 (C

q

), 133.9 (C

q

), 133.8 (C

_q

), 133.7 (C

_q

), 129.8 (CH), 129.6 (CH), 129.3 (CH), 129.2 (CH), 129.1 (CH), 128.0 (CH), 127.9 (CH), 127.7 (CH), 127.6 (CH), 126.2 (CH), 126.1 (CH), 125.5 (CH), 125.4 (CH), 125.0 (CH), 124.9 (CH), 123.6 (CH), 123.5 (CH), 120.6 (C

q

), 120.4 (C

q

), 116.0 (CH), 115.9 (CH), 72.8 (CH

2

), 72.7 (CH

2

), 70.7 (CH

2

), 70.4 (CH

2

), 70.2 (CH

2

), 69.7 (CH

2

), 69.6 (CH

₂

), 33.8 (C

_q

), 33.7 (C

_q

), 31.6 (CH

₃

), 31.4 (CH

₃

), 31.1 (CH

₃

), 31.0

133

General Procedure for the Synthesis of rac-42b、(S)-(-)-42b.

OH O O

AcOH, THF/MeOH (v/v = 4/5) rt. 12 h

AcOH, THF/MeOH (v/v = 4/5) rt. 18 h

134

The stirred mixture of the substrate rac-41a or rac-41b or (S)-(-)-41b (rac-41a: 60 mg, 0.04 mmol; rac-41b: 100 mg, 0.07 mmol;

(S)-(-)-41b: 100 mg, 0.07 mmol), 10% Pd/C (en) (90% of the weight of the substrate; 70% of the weight of the substrate) in MeOH, and THF (v/v

= 4/5, 27 mL; v/v = 4/5, 45 mL) was hydrogenated at ordinary pressure (balloon) and room temperature for 12 h or 18 h. The Pd/C was removed by suction filtration, and the solvent was removed under reduced pressure.

The crude material was purified over silica gel column elutiong with hexane/ethyl acetate (v/v = 5/1) to give the compound rac-42a or rac-42b or (S)-(-)-42b (rac-42a: 33.7 mg, 65%; rac-42b: 71.0 mg, 91%;

(S)-(-)-42b: 64.0 mg, 82%) as a white solid.

Data for rac-42b:

¹

H NMR (CDCl

3

, 300MHz) δ

_H

8.60 (s, 1H, ArOH), 8.56 (s, 1H, ArOH), 7.92-7.83 (m, 4H, ArH), 7.45 (d, J = 9.0 Hz, 1H, ArH), 7.35 (d, J = 9.0 Hz, 1H, ArH), 7.31-6.90 (m, 14H), 4.53 (d, 1H, J = 13 Hz, ArCH

₂

Ar), 4.40 (d, 1H, J = 12.6 Hz, ArCH

₂

Ar), 4.38 (d, 1H, J = 12.6 Hz, ArCH

2

Ar), 4.281-3.38 (m, 24H, OCH

2

O), 3.29 (d, 1H, J = 12.6 Hz, ArCH

2

Ar), 1.21-1.08 (m, 36H, ArC(CH

3

)

3

Data for (S)-(-)-42b:

¹

H NMR (CDCl

3

, 300MHz) δ

_H

8.60 (s, 1 H, ArOH), 8.56 (s, 1 H, ArOH), 7.92-7.83 (m, 4 H, ArH), 7.45 (d, J = 9.0 Hz, 1 H, ArH), 7.35 (d, J = 9.0 Hz, 1 H, ArH), 7.31-6.90 (m, 14 H), 4.53 (d, 1 H, J

= 13 Hz, ArCH

₂

Ar), 4.40 (d, 1 H, J = 12.6 Hz, ArCH

₂

Ar), 4.38 (d, 1 H, J

= 12.6 Hz, ArCH

2

Ar), 4.281-3.38 (m, 24 H, OCH

2

O), 3.29 (d, 1 H, J

= 12.6 Hz, ArCH

2

Ar), 1.21-1.08 (m, 36 H, ArC(CH

3

)

3

135

General Procedure for the Synthesis of (S)-(-)-42a and (S)-(-)-42b.

OHO O OH

OH OH HO OH

O O

OTs OTs

NaH, CH3CN, 70^oC, 48 h

O O

O O n n

(S)-(-)-42a n = 1 50%

(S)-(-)-42b n = 2 60%

n n

(S)-(-)-38a n = 1 (S)-(-)-38b n = 2

20

A mixture of tert-butylcalix[4]arene 20 (1.18 g, 1.8 mmol; 1.00 g, 1.5 mmol) and sodium hydride ( 0.22 g, 8.9 mmol; 0.19 g, 7.7 mmol) in acetonitrile (240 mL; 200 mL) was stirred under N

2

system at 70

^o

C for 1 h. Then, compound (S)-(-)-38a or (S)-(-)-38b ((S)-(-)-38a: 1.70 g, 2.2 mmol; (S)-(-)-38b: 1.52 g, 1.8 mmol) was added to the solution at 70

^o

C for 2 days. Then a small amount of 10% HCl was added to quench the reaction. The solvent was removed under reduced pressure, and the residue was partitioned between water and CH

2

. The organic layer was dried over anhydrous MgSO

4

. The crude material was purified over silica gel column elutiong with hexane/ethylacetate ((S)-(-)-42a: v/v = 15/1;

(S)-(-)-42b: v/v = 2/1) to give the compound (S)-(-)-42a or (S)-(-)-42b ((S)-(-)-42a: 0.81g, 50%; (S)-(-)-42b: 1.12g, 60%) as a white solid.

Data for(S)-(-)-42a:

¹

H NMR (CDCl

3

, 300MHz) δ

_H

8.78 (S, 1 H, ArOH), 8.21 (s, 1 H, ArOH), 7.97 (d, J = 9.0 Hz, 1 H, ArH), 7.92-7.81 (m, 3H, ArH), 7.57 (d, J = 9.0 Hz, 1H, ArH), 7.49 (d, J = 9.0 Hz, 1H, ArH), 7.34-7.13 (m, 6H), 7.11 (d, J = 2.1 Hz, 1H, ArH), 7.06 (d, J = 2.1 Hz, 1H, ArH), 6.98 (d, J = 2.1 Hz, 1H, ArH), 6.95 (d, J = 2.1 Hz, 1H, ArH), 6.87

136

(d, J = 2.3 Hz, 1H, ArH) 6.85 (d, J = 2.3 Hz, 1H, ArH), 6.69 (d, J = 2.5 Hz, 1H, ArH), 6.67 (d, J = 2.5 Hz, 1H, ArH), 4.61-4.41 (m, 3H, ArCH

2

Ar, OCH

2

O), 4.33-3.63 (m, 14H, ArCH

2

Ar, OCH

2

O), 3.55-3.51 (m, 3H, OCH

₂

O), 3.31-3.21 (m, 4H, ArCH

₂

Ar), 1.26 (s, 1H, ArC(CH

₃

)

₃

), 1.23 (s, 1H, ArC(CH

3

)

3

), 1.11 (s, 1H, ArC(CH

3

)

3

), 0.91 (s, 1H, ArC(CH

3

)

3

);

¹³

C-NMR (75.4 MHz, CDCl

3

) δ 154.5 (C

_q

), 154.0 (C

q

), 152.0 (C

q

), 151.5 (C

q

), 150.0 (C

q

), 147.6 (C

q

), 146.6 (C

q

), 145.3 (C

q

), 142.4 (C

_q

), 141.5 (C

_q

), 134.9(C

_q

), 134.1 (C

_q

), 134.0 (C

_q

), 133.6 (C

_q

), 133.1 (C

q

), 132.5 (C

q

), 129.8 (C

q

), 129.6 (CH), 129.5 (C

q

), 129.2 (C

q

), 129.1 (CH), 128.0 (CH), 127.9 (CH), 127.8 (C

q

), 127.5 (C

q

), 127.2 (C

q

), 126.6 (CH), 126.2 (CH), 126.0 (CH), 125.4 (CH), 125.3 (CH), 125.2 (CH), 125.0 (CH), 125.0 (CH), 124.9 (CH), 124.8 (CH), 123.8 (CH), 123.4 (CH), 121.3 (C

_q

), 119.7 (C

_q

), 117.0 (CH), 114.9 (CH), 74.9 (CH

₂

), 74.5 (CH

2

), 70.8 (CH

2

),70.6 (CH

2

), 70.4 (CH

2

), 70.0 (CH

2

), 69.9 (CH

2

), 69.1 (CH

2

), 35.4 (C

q

), 34.1 (C

q

), 33.8 (C

q

), 33.7 (C

q

), 32.4 (CH

2

), 32.0 (CH

2

), 31.6 (CH

3

), 31.4 (CH

3

), 31.3 (CH

3

), 31.0 (CH

3

), 30.9 (CH

2

), 30.8 (CH

₂

); mp 166-170

^o

C; [α]

_D ²⁵

= -115.5 (c = 0.01, CHCl

₃

). FAB-MS: m/z (%) 1098 (M + Na

⁺

, 5), 1075 (M

⁺

, 32), 611 (40), 337 (58), 313 (100).

Data for(S)-(-)-42b:

¹

H NMR (CDCl

3

, 300MHz) δ

H

8.60 (s, 1H, ArOH), 8.56 (s, 1H, ArOH), 7.92-7.83 (m, 4H, ArH), 7.45 (d, J = 9.0 Hz, 1H, ArH), 7.35 (d, J = 9.0 Hz, 1H, ArH), 7.31-6.90 (m, 14H), 4.53 (d, 1H, J = 13 Hz, ArCH

2

Ar), 4.40 (d, 1H, J = 12.6 Hz, ArCH

2

Ar), 4.38 (d, 1H, J = 12.6 Hz, ArCH

2

Ar), 4.281-3.38 (m, 24H, OCH

2

O), 3.29 (d, 1H, J = 12.6 Hz, ArCH

₂

Ar), 1.21-1.08 (m, 36H, ArC(CH

₃

)

₃

);

¹³

C-NMR (75.4 MHz, CDCl

3

) δ 154.58 (C

_q

), 154.43 (C

q

), 151.64 (C

q

), 151.59 (C

q

), 148.97 (C

q

), 148.83 (C

q

), 146.13 (C

q

), 142.07 (C

q

), 142.01 (C

q

), 134.05 (C

q

), 133.99 (C

q

), 133.76 (C

q

), 133.71 (C

q

), 133.71 (C

q

), 133.55 (C

q

), 133.51 (C

_q

), 129.47 (CH), 129.42 (CH), 129.37 (CH), 128.71 (C

_q

137

128.54 (C

q

), 127.89 (CH), 127.82 (CH), 127.78 (CH), 127.74 (CH), 126.19 (CH), 126.15 (CH), 125.85 (CH), 125.75 (CH), 125.48 (CH), 125.36 (CH), 125.12 (CH), 125.05 (CH), 123.61 (CH), 120.62 (C

q

), 120.59 (C

_q

), 116.51 (CH), 115.95 (CH), 74.61 (CH

₂

), 70.83 (CH

₂

), 70.75 (CH

2

), 70.65 (CH

2

), 70.31 (CH

2

), 70.26 (CH

2

), 70.15 (CH

2

), 69.98 (CH

2

), 69.82 (CH

2

), 33.95 (C

q

), 33.81 (C

q

), 32.54 (CH

2

), 31.81 (CH

2

), 31.53 (CH

3

), 31.51(CH

3

), 31.25(CH

3

), 31.01 (CH

2

); mp 125-129

^o

C; [α]

D

25

= -87.9 (c = 0.011, CHCl

₃

) FAB-MS: m/z (%) 1186 (M + Na

⁺

, 40), 1163 (M

⁺

, 9), 612 (27), 337 (53), 313 (100).

General Procedure for the Synthesis of (S)-(-)-43a, (S)-(-)-43b.

O OO O

Br O

NaH, THF, 70⁰C, 24 h (10 eq.)

O O O

O O

(S)-(-)-43a n = 1 93%

(S)-(-)-43b n = 2, 86%

n n

OHO O OH

O O

O O n n

(S)-(-)-42a n = 1 (S)-(-)-42b n = 2

A mixture of compound (S)-(-)-42a or (S)-(-)-42b ((S)-(-)-42a: 0.2 g, 0.19 mmol; (S)-(-)-42b: 0.5 g, 0.42 mmol) and sodium hydride (44 mg, 1.83 mmol; 0.1 g, 4.15 mmol) in acetonitrile (20 mL; 50 mL) was stirred vigorously at 70

^o

C for 1 h. Then, ethyl 2-bromoacetate (310 mg, 1.83 mmol; 0.7 g, 4.15 mmol) was added to the solution at 70

^o

C for 1 day. The solvent was removed under reduced pressure, and the residue was purified over silica gel column elutiong with hexane/ethylacetate ((S)-(-)-43a: v/v = 4/1; (S)-(-)-43b: v/v = 1/1) to give the compound

138

(S)-(-)-43a or (S)-(-)-43a ((S)-(-)-43a: 0.21 g, 93%; (S)-(-)-43b: 0.45 g, 86%) as a white solid.

Data for(S)-(-)-43a:

¹

H NMR (CDCl

3

, 300MHz) δ

_H

7.98-7.82 (m, 4H, ArH), 7.52-7.45 (m, 2H, ArH), 7.34-7.05 (m, 6H, ArH), 6.81-6.75 (m, 8H, ArH), 4.92-4.83 (m, 2H, OCH

2

C(O)), 4.69-4.58 (m, 2H, OCH

2

C(O)), 4.52-4.31 (m, 3H, ArCh

₂

Ar, OCH

₂

O) , 4.26-3.58 (m, 21H, ArCh

₂

Ar, OCH

₂

O), 3.20-3.11 (m, 4 H, ArCh

₂

Ar), 1.31-1.25 (m, 3H, OCH

2

3

), 1.22-1.17 (m, 3H, OCH

2

3

), 1.10 (s, 9H, ArCCH

3

), 1.08 (s, 9H, ArC(CH

3

)

3

), 1.06 (s, 9H, ArCCH

3

), 1.05 (s, 9H, ArCCH

3

);

¹³

C-NMR (75.4 MHz, CDCl

3

) δ 171.7 (C

q

), 170.8 (C

q

), 170.5 (C

q

), 170.4 (C

q

), 154.6 (C

_q

), 154.2 (C

_q

), 153.3 (C

_q

), 153.1 (C

_q

), 145.0 (C

_q

), 144.9 (C

_q

), 144.8 (C

q

), 144.7 (C

q

), 134.2 (C

q

), 134.0 (C

q

), 133.9 (C

q

), 133.8 (C

q

), 133.5 (C

q

), 133.3 (C

q

), 133.1 (C

q

), 129.4 (CH), 129.2 (CH), 129.1 (CH), 127.8 (CH), 127.7 (CH), 126.3 (CH), 126.1 (CH), 125.5 (CH), 125.4 (CH), 125.3 (CH), 125.2 (CH), 125.0 (CH), 124.8 (CH), 123.4 (CH), 120.2 (C

q

), 120.0 (C

q

), 116.3 (CH), 114.9 (CH), 72.9 (CH

2

), 71.7 (CH

2

), 71.6 (CH

2

), 70.4 (CH

2

), 70.0 (CH

2

), 69.5 (CH

2

), 69.3 (CH

2

), 69.0 (CH

2

), 68.6 (CH

2

), 60.6 (CH

2

), 60.3 (CH

2

), 55.1 (CH

2

), 33.8 (C

q

), 31.7 (CH

3

), 31.3 (CH

3

), 31.1 (CH

2

), 30.9 (CH

2

), 14.1 (CH

3

); mp 115-117

^o

C; [α]

D 25

= -56.5 (c = 0.001, CHCl

₃

). FAB-MS: m/z (%) 1286 (M + K

⁺

, 5), 1270 (M + Na

⁺

, 100), 611 (41), 607 (42), 313 (40).

Data for(S)-(-)-43b:

¹

H NMR (CDCl

3

, 300MHz) δ

_H

7.94 (d, J = 8.9 Hz, 1H, ArH), 7.87-7.81 (m, 3H, ArH), 7.47 (d, J = 8.9 Hz, 1H, ArH), 7.38-7.08 (m, 7H, ArH), 6.82-6.78 (m, 8H, ArH), 4.88-4.59 (m, 7H, OCH

2

C(O), ArCh

2

Ar), 4.44 (d, J = 12.6 Hz, 1H, ArCh

2

Ar), 4.21-3.38 (m, 28H, OCH

₂

O, ArCh

₂

Ar, OCH

₂

₃

), 3.22-3.09 (m, 4H, ArCh

₂

Ar ,

139

OCH

2

3

), 1.29-1.19 (m, 6H, OCH

2

3

), 1.09-1.07 (m, 36H, ArCH

3

);

13

C-NMR (75.4 MHz, CDCl

3

) δ 170.51 (C

q

), 154.49 (C

q

), 153.17 (C

q

), 144.99 (C

q

), 144.82 (C

q

), 144.78 (C

q

), 134.17 (C

q

), 134.09 (C

q

), 134.02 (C

_q

), 133.82 (C

_q

), 133.68 (C

_q

), 133.51 (C

_q

), 133.39 (C

_q

), 133.26 (C

_q

), 133.18 (C

q

), 129.44 (CH), 129.40 (CH), 129.29 (CH), 129.17 (CH), 127.82 (CH), 127.80 (CH), 126.21 (CH), 126.16 (CH), 125.49 (CH), 125.39 (CH), 125.32 (CH), 125.07 (CH), 124.97 (CH), 123.65 (CH), 123.56 (CH), 120.76 (C

_q

), 120.47 (C

_q

), 116.29 (CH), 116.21 (CH), 72.93 (CH

2

), 72.72 (CH

2

), 71.70 (CH

2

), 71.59 (CH

2

), 70.73 (CH

2

), 70.61 (CH

2

), 70.46 (CH

2

), 70.34 (CH

2

), 70.19 (CH

2

), 70.08 (CH

2

), 69.99 (CH

2

), 69.82 (CH

2

), 69.65 (CH

2

), 60.42 (CH

2

), 33.85 (C

q

), 33.83 (C

q

), 33.81 (C

q

), 31.43 (CH

₃

), 31.42 (CH

₃

), 31.37 (CH

₂

), 31.25 (CH

₂

), 30.94 (CH

₂

), 14.24 (CH

₃

); mp 100-103

^o

C; [α]

_D ²⁵

= -59.4 (c = 0.006, CHCl

₃

). FAB-MS: m/z (%) 1376 (M + K

⁺

, 2), 1359 (M + Na

⁺

, 100), 608 (68).

General Procedure for the Synthesis of (S)-(-)-44a and (S)-(-)-44b.

NaOH THF/H₂O (v/v = 2/1),

reflux, 18 h

HO O HO O

O O O

O O

(S)-(-)-44a n = 1, 92%

(S)-(-)-44b n = 2, 90%

n n

O OO O

O O O

O O

(S)-(-)-43a n = 1 (S)-(-)-43b n = 2

n n

A mixture of compound (S)-(-)-43a or (S)-(-)-43b ((S)-(-)-43a: 150 mg, 0.12 mmol; (S)-(-)-43b: 100 mg, 0.075 mmol) and sodium hydroxide (150 mg, 3.75 mmol; 150 mg, 3.75 mmol) in THF and water (v/v =

140

2/1,48 mL; v/v = 2/1, 30mL) was stirred vigorously and heated at reflux for 18 h. The solvent was removed under reduced pressure, and the crude in water was partitioned between 10% HCl (50 mL) and CH

2

. The organic layer was dried over anhydrous MgSO

₄

. The crude material was purified over silica gel column elutiong with hexane/acetone ((S)-(-)-44a:

v/v = 3/1; (S)-(-)-44b: v/v = 1/3) containing increasing amounts of CH

3

OH from 0 to 50%) to give the compound (S)-(-)-44a or (S)-(-)-44a ((S)-(-)-44a: 0.14 g, 92%; (S)-(-)-44b: 0.09 g, 90%) as a white solid.

Data for(S)-(-)-44a:

¹

H NMR (CDCl

3

, 300MHz) δ

H

7.83-7.70(m, 4H, ArH), 7.31-6.91 (m, 16H, ArH), 4.89-4.57 (m, 4H, ArCh

2

A, OCH

2

C(O)), 4.36-3.11 (m, 24H, ArCh

₂

A, OCH

₂

C(O), OCH

₂

O), 1.18 (s, 9H, ArCCH

3

), 1.13 (s, 9H, ArCCH

3

), 1.08 (s, 9H, ArCCH

3

), 1.03 (s, 9H, ArC(CH

3

)

3

);

¹³

C-NMR (75.4 MHz, CDCl

3

) δ 175.22 (C

q

), 154.44 (C

q

), 153.93 (C

q

), 151.34 (C

q

), 150.26 (C

q

), 149.81 (C

q

), 149.25 (C

q

), 146.68 (C

_q

), 146.61 (C

_q

), 146.08 (C

_q

), 135.79 (C

_q

), 135.25 (C

_q

), 134.86 (C

_q

), 134.47 (C

q

), 134.11 (C

q

), 133.92 (C

q

), 130.18 (CH), 128.95 (CH), 128.83 (CH), 128.10 (CH), 127.64 (CH), 126.06 (CH), 125.86 (CH), 125.26 (CH), 124.40 (CH), 123.28 (CH), 122.82 (CH), 120.55 (C

q

), 118.62 (C

q

), 114.96 (CH), 114.57 (CH), 113.87 (CH), 76.05 (CH

2

), 75.73 (CH

2

), 75.30 (CH

₂

), 69.97 (CH

₂

), 69.28 (CH

₂

), 68.91 (CH

₂

), 33.94 (C

_q

), 33.85 (C

_q

), 33.62 (C

q

), 31.35 (CH

3

), 31.22 (CH

3

), 29.96 (CH

2

), 29.63 (CH

2

), 29.30 (CH

2

); mp 254-256

^o

C; [α]

D

= -92.0 (c = 0.005, CHCl

3

); [α]

D

25

= -92.0 (c

= 0.005, CHCl

3

). FAB-MS: m/z (%) 1252 (M + Na

⁺

+ K

⁺

, 16), 1236 (M + 2Na

⁺

, 40), 1213 (M + Na

⁺

, 29), 607 (100), 239 (51).

Data for(S)-(-)-44b:

¹

H NMR (CDCl

3

, 300MHz) δ

H

7.93 (d, J = 9.0 Hz, 1H, ArH), 7.85-7.78 (m, 3H, ArH), 7.53 (d, J = 9.0 Hz, 1H, ArH), 7.42 (d,

141 J = 8.9 Hz, 1H, ArH), 7.32-6.99 (m, 14H, ArH), 4.69 (d, J = 12.2 Hz, 1H,

ArCh

2

Ar), 4.39-3.13 (m, 37H, ArCh

2

Ar, OCH

2

C(O), OCH

2

O), 1.14-1.10 (m, 36H, ArC(CH

3

)

3

);

¹³

C-NMR (75.4 MHz, CDCl

3

) δ 174.46 (C

_q

), 174.39 (C

_q

), 154.49 (C

_q

), 154.17 (C

_q

), 150.20 (C

_q

), 149.77 (C

_q

), 149.49 (C

q

), 149.20 (C

q

), 146.87 (C

q

), 146.66 (C

q

), 135.20 (C

q

), 134.54 (C

q

), 134.48 (C

q

), 134.44 (C

q

), 134.38 (C

q

), 134.17 (C

q

), 134.02 (C

q

), 133.96 (C

q

), 129.48 (CH), 129.41 (C

q

), 129.19 (C

q

), 128.92 (CH), 127.90 (CH), 127.64 (CH), 126.17 (CH), 125.68 (CH), 125.49 (CH), 125.34 (CH), 125.22 (CH), 125.11 (CH), 125.05 (CH), 123.69 (CH), 123.42 (CH), 121.04 (C

q

), 119.73 (C

q

), 116.80 (CH), 115.12 (CH), 76.01 (CH

2

), 75.85 (CH

2

), 75.23 (CH

2

), 74.78 (CH

2

), 70.46 (CH

2

), 70.38 (CH

2

), 70.17 (CH

₂

), 70.11 (CH

₂

), 69.97 (CH

₂

), 69.87 (CH

₂

), 69.44 (CH

₂

), 68.63 (CH

₂

), 68.38 (CH

₂

), 34.00 (C

_q

), 33.96 (C

_q

), 31.54 (CH

₃

), 31.31 (CH

₃

), 31.26 (CH

3

), 30.23 (CH

2

), 30.11 (CH

2

), 29.91 (CH

2

), 29.48 (CH

2

); mp 218-220

o

C; [α]

D

25

= -72.4 (c = 0.013, CHCl

3

). FAB-MS: m/z (%) 1341 (M + Na

⁺

+ K

⁺

, 7), 1325 (M + 2Na

⁺

, 9), 1303 (M + Na

⁺

, 15), 624 (45), 608 (43), 307 (100).

25,26-[(S)-(-)-2,2'-binaphthyl-crown-8]-27,28-di-(N,N-diethylacetami de)-p-tertbutylcalix[4]arene(S)-(-)-45.

N ON O

O O O

O O

O O N

O Cl

NaH, THF, 70⁰C, 48 h

92%

(S)-(-)-45 n = 2

n n

OHO O OH

O O

O O n n

(S)-(-)-42b n = 2

(10 eq.)

142

A mixture of compound (S)-(-)-42b (0.10 g, 0.09 mmol) and sodium hydride (0.02 g, 0.86 mmol) in acetonitrile (10 mL) was stirred vigorously at 70

^o

C for 1 h. Then, 2-chloro-N,N-diethylacetamide (0.17 g, 0.86 mmol) was added to the solution at 70

^o

C for 3 day. The solvent was removed under reduced pressure, and the residue was purified over silica gel column elutiong with hexane/ethylacetate (v/v = 1/3) to give 0.11 g (92%) of the title compound as a white solid.

¹

H NMR (CDCl

3

, 300MHz) δ

_H

7.96 (d, J = 9.0 Hz, 1H, ArH), 7.88-7.78 (m, 3H, ArH), 7.46 (d, J = 9.0 Hz, 1H, ArH), 7.38-7.08 (m, 15H, ArH), 4..72-4.58 (m, 3H, OCH

2

C(O)), 4.4 (d, 1H, J = 12.2 Hz, ArCH

2

Ar), 4.32-4.00 (m, 11H, OCH

2

O, ArCH

2

Ar), 3.92-3.19 (m, 29H, OCH

2

O, ArCH

2

Ar), 1.23-1.14 (m, 48H, ArC(CH

₃

)

₃

, NCH

₂

₃

);

¹³

C-NMR (75.4 MHz, CDCl

₃

) δ 166.99 (C

_q

), 166.89 (C

_q

), 154.38 (C

_q

), 154.16 (C

_q

), 150.03 (C

_q

), 149.99 (C

_q

), 149.56 (C

q

), 149.33 (C

q

), 148.05 (C

q

), 147.22 (C

q

), 147.14 (C

q

), 134.84 (C

q

), 134.09 (C

q

), 133.99 (C

q

), 133.92 (C

q

), 133.87 (C

q

), 129.34 (CH), 129.24 (CH), 129.20 (CH), 129.13 (CH), 127.70 (CH), 126.22 (CH), 126.14 (CH), 125.86 (CH), 125.70 (CH), 125.51 (CH), 125.45 (CH), 125.37 (CH), 1215.32 (CH), 123.62 (CH), 120.68 (C

q

), 120.19 (C

q

), 116.40 (CH), 115.41 (CH), 75.64 (CH

2

), 75.16 (CH

2

), 73.67 (CH

2

), 70.75 (CH

2

), 70.41 (CH

2

), 69.86 (CH

2

), 69.75 (CH

2

), 69.41 (CH

2

), 69.07 (CH

2

), 68.46 (CH

₂

), 40.74 (CH

₂

), 40.18 (CH

₂

), 34.04 (C

_q

), 33.96 (C

_q

), 31.18 (CH

₃

), 29.97 (CH

₂

), 29.77 (CH

₂

), 29.57 (CH

₂

), 14.10 (CH

₃

), 13.11 (CH

₃

), 13.01 (CH

3

); mp 120-123

^o

C; [α]

D

25

= -50.9 (c = 0.011, CHCl

3

). FAB-MS:

m/z (%) 1428 (M + K ⁺

, 5), 1413 (M + Na

⁺

, 100), 608 (100).

143

25,26-[rac-2,2'-binaphthyl-crown-8]-27,28-dipropyl-p-tertbutylcalix[4 ]arene (S)-(-)-46.

NaH, CH₃CN, 70^oC, 24 h

98%

O O O

O O

(S)-(-)-46 n = 2

n n

OHO O OH

O O

O O n n

(S)-(-)-42b n = 2

A mixture of compound (S)-(-)-42b (0.40 g, 0.34 mmol) and sodium hydride (0.08 g, 3.40 mmol) in acetonitrile (50 mL) was stirred vigorously at 70

^o

C for 1 h. Then, propyl iodide (0.34 mL, 3.40 mmol) was added to the solution at 70

^o

C for 1 day. The solvent was removed under reduced pressure, and the residue was purified over silica gel column elutiong with hexane/ethylacetate (v/v = 2/1) to give 0.42 g (98%) of the title compound as a white solid.

¹

H NMR (CDCl

3

, 300MHz) δ

H

7.93 (d, J = 9.0 Hz, 1H, ArH), 7.86-7.80 (m, 3H, ArH), 7.46 (d, J = 9.0 Hz, 1H, ArH), 7.38-7.27 (m, 3H, ArH), 7.23-7.09 (m, 4H, ArH), 6.83-6.76 (m, 8H, ArH), 4.52-4.44 (m, 3H, OCH

2

3

), 4.37 (d, 1H, J

= 13 Hz, ArCH

2

Ar), 3.63-3.30 (m, 12H, OCH

2

O, ArCH

2

Ar), 3.12 (d, 4H, J = 13 Hz ArCH

₂

Ar), 2.06-1.96 (m, 4H, OCH

₂

₃

), 1.10-1.08 (m, 36H, ArC(CH

3

)

3

), 1.00-0.98 (m, 6H, OCH

2

3

);

¹³

C-NMR (75.4 MHz, CDCl

3

) δ 154.40 (C

_q

), 153.554 (C

q

), 153.47 (C

q

), 153.34 (C

q

), 153.19 (C

q

), 144.56 (C

q

), 144.51 (C

q

), 144.22 (C

q

), 144.16 (C

q

), 134.04 (C

q

), 133.98 (C

q

), 133.89 (C

q

), 133.85 (C

q

), 133.80 (C

q

), 133.64 (C

q

), 133.56 (C

_q

), 129.40 (C

_q

), 129.36 (C

_q

), 129.27 (CH), 129.13 (CH), 127.79

144

(CH), 127.76 (CH), 126.20 (CH), 126.14 (CH), 125.44 (CH), 125.35 (CH), 124.91 (CH), 124.87 (CH), 124.80 (CH), 123.63 (CH), 123.54 (CH), 120.71 (C

q

), 120.42 (C

q

), 116.17 (CH), 76.58 (CH

2

), 72.98 (CH

2

), 72.71 (CH

₂

), 70.60 (CH

₂

), 70.55 (CH

₂

), 70.53 (CH

₂

), 70.41 (CH

₂

), 70.24 (CH

2

), 70.12 (CH

2

), 69.90 (CH

2

), 69.83 (CH

2

), 69.72 (CH

2

), 69.63 (CH

2

), 33.81 (C

q

), 33.77 (C

q

), 33.74 (C

q

), 31.43 (CH

3

), 31.40 (CH

3

), 30.96 (CH

2

), 30.19 (CH

2

), 23.25 (CH

2

), 10.39 (CH

3

), 10.37 (CH

3

); mp 120-123

^o

[α]

_D ²⁵

= -52.7 (c = 0.01, CHCl

₃

). FAB-MS: m/z (%) 1286 (M + K

⁺

, 4), 1270 (M + Na

⁺

, 100), 612 (47).

25,26-[(S)-(-)-2,2'-binaphthyl-crown-8]-27,28-dihydroxy-calix[4]aren e (S)-(-)-47.

OHOH HO OH

21

OHO O OH

O O

OTs OTs

NaH, CH₃CN, 70^oC, 48 h

O O

O O n n

(S)-(-)-47 n = 2 85%

n n

(S)-(-)-38b n = 2

A mixture of calix[4]arene 21 (0.28 g, 0.66 mmol) and sodium hydride ( 0.08 g, 3.4 mmol) in acetonitrile (90 mL) was stirred under N

2

system at 70

^o

C for 1 h. Then, compound (S)-(-)-38b (0.65 g, 0.76 mmol) was added to the solution at 70

^o

C for 2 days. Then a small amount of 10% HCl was added to quench the reaction. The solvent was removed under reduced pressure, and the residue was partitioned between water and CH

2

. The organic layer was dried over anhydrous MgSO

4

. The crude material was purified over silica gel column elutiong with

145

hexane/ethylacetate (v/v = 5/1) to give 0.52 g (83%) of the title compound as a white solid.

¹

H NMR (CDCl

3

, 300MHz) δ

H

8.7351 (s, 1H, ArOH), 8.649 (s, 1H, ArOH), 7.95-7.83 (m, 4H, ArH), 7.46 (d, J = 9.0 Hz, 1H, ArH), 7.36-7.13 (m, 8H, ArH), 7.02-6.93 (m, 8H, ArH), 6.82-6.75 (m, 2H, ArH), 6.72-6.59 (m, 2H, ArH), 4.61 (d, 1H, J = 12.7 Hz, ArCH

2

Ar), 4.44 (d, 1H, J = 12.6 Hz, ArCH

2

Ar), 4.38 (d, 1H, J = 12.6 Hz, ArCH

2

Ar), 4.44-3.81 (m, 16H, OCH

2

O, ArCH

2

Ar), 3.65-3.53 (m, 17H, OCH

₂

O, ArCH

₂

Ar) ;

¹³

C-NMR (75.4 MHz, CDCl

₃

) δ 154.52 (C

_q

), 154.38 (C

q

), 153.80 (C

q

), 153.74 (C

q

), 151.17 (C

q

), 151.02 (C

q

), 134.68 (C

q

), 134.53 (C

q

), 134.46 (C

q

), 134.36 (C

q

), 134.01 (C

q

), 129.44 (CH), 129.35 (CH), 129.19 (CH), 129.15 (CH), 128.99 (CH), 128.95 (CH), 128.88 (CH), 128.79 (CH), 128.71 (CH), 128.61 (CH), 128.54 (CH), 128.47 (C

_q

), 128.39 (CH), 128.16 (CH), 128.05 (CH), 127.85 (CH), 127.78 (CH), 126.19 (CH), 125.42 (CH), 125.34 (CH), 124.42 (CH), 124.35 (CH), 123.63 (CH), 120.01 (C

q

), 120.57 (C

q

), 120.15 (CH), 120.09 (CH), 116.37 (CH), 115.88 (CH), 74.87 (CH), 74.77 (CH), 70.83 (CH), 70.74 (CH), 70.70 (CH), 70.59 (CH), 70.12 (CH), 69.97 (CH), 69.94 (CH), 69.79 (CH), 31.77 (CH

2

), 31.27 (CH

2

), 30.48 (CH

2

); mp 119-122

^o

C; [α]

D

25

= -98.7 (c = 0.011, CHCl

3

). FAB-MS: m/z (%) 962 (M + Na

⁺

, 5), 939 (M

⁺

, 27), 308 (100).

General Procedure for the Synthesis of (S)-(-)-48a and (S)-(-)-48b.

OHO O O

O O

O O O

O O

Cs₂CO₃, DMF, 70^oC, 24 h +

Br O

O OHO O

O O

(S)-(-)-42a (S)-(-)-48a 34% (S)-(-)-48b 34%

146

A mixture of compound (S)-(-)-42a (0.3 g, 0.28 mmol) and caesium carbonate (90.9 mg, 0.28 mmol) in acetonitrile (20 mL) was stirred vigorously at 70

^o

C for 1 h. Then, ethyl 2-bromoacetate (51.2 mg, 0.31 mmol) was added to the solution at 70

^o

C for 3 hours. Then a small amount of 10% HCl was added to quench the reaction. The solvent was removed under reduced pressure, and the residue was partitioned between water and CH

2

. The organic layer was dried over anhydrous MgSO

4

. The crude material was purified over silica gel column elutiong with hexane/ethylacetate (v/v = 10/1) to give the compound (S)-(-)-48a 0.11g (34%) and the compound (S)-(-)-48b 0.11g (34%) as a white solid.

Data for (S)-(-)-48a: R

_f = 0.45 (silica, hexane/ethyl acetate = 5/1) ¹

H NMR (CDCl

3

, 300MHz) δ

H

7.99-7.82 (m, 4H, ArH), 7.54 (d, J = 9.0 Hz, 1H, ArH), 7.49 (d, J = 9.0 Hz, 1H, ArH), 7.33-7.01 (m, 10H, ArH), 6.66-6.63 (m, 2H, ArH), 6.45-6.42 (m, 2H, ArH), 6.10 (s, 1H, ArOH), 4.52-4.05 (m, 15H, ArCH

₂

Ar, ArOCH

₂

C(O), OCH

₂

O), 3.82-3.62 (m, 8H, OCH

2

O), 3.36-3.16 (m, 5H, OCH

2

O, C(O)CH

2

3

), 1.32 (2s, 18H, ArC(CH

3

)

3

), 1.16 (t, J = 7.1 Hz, 3H, C(O)CH

2

3

), 0.91 (s, 9H, ArC(CH

3

)

3

), 0.75 (s, 9H, ArC(CH

3

)

3

);

¹³

C-NMR (75.4 MHz, CDCl

3

) δ 169.54 (C

q

), 154.45 (C

q

), 154.35 (C

q

), 153.47 (C

q

), 152.30 (C

q

), 150.62 (C

_q

), 150.39 (C

_q

), 146.00 (C

_q

), 145.76 (C

_q

), 145.13 (C

_q

), 141.04 (C

_q

), 135.91 (C

q

), 135.30 (C

q

), 134.12 (C

q

), 134.04 (C

q

), 132.65 (C

q

), 131.89 (C

q

), 131.83 (C

q

), 131.69 (C

q

q), 129.31 (C

q

), 129.45 (CH), 129.20 (C

q

), 128.84 (CH), 127.98 (CH), 127.87 (C

q

), 127.72 (CH), 126.20 (CH), 126.17 (CH), 125.74 (CH), 125.45 (CH), 125.41 (CH), 125.28 (CH), 125.18 (CH), 125.02 (CH), 124.89 (CH), 124.68 (CH), 123.43 (CH), 120.22 (C

q

), 119.81 (C

q

), 116.26 (CH), 115.25 (CH), 75.23 (CH

2

), 72.03 (CH

2

), 71.69 (CH

2

), 70.29 (CH

2

), 70.06 (CH

2

), 69.84 (CH

2

), 69.65 (CH

2

), 69.33 (CH

₂

), 69.07 (CH

₂

), 60.77 (CH

₂

), 34.09 (C

_q

), 33.78 (C

_q

), 33.75 (C

_q

147

q), 33.55 (C

q

), 31.73 (CH

3

), 31.62 (CH

3

), 31.33 (CH

2

), 31.14 (CH

2

), 31.01 (CH

3

), 30.97 (CH

3

), 30.80 (CH

2

), 14.08 (CH

3

); mp 142-145

^o

[α]

D 25

= -62.0 (c = 0.005, CHCl

3

). FAB-MS: m/z (%) 1185 (M + Na

⁺

, 100), 1161 (M

⁺

, 11), 612 (52).

Data for (S)-(-)-48b: R

f

= 0.36 (silica, hexane/ethyl acetate = 5/1)

¹

H NMR (CDCl

₃

, 300MHz) δ

_H

7.93 (d, J = 9.0 Hz, 1H, ArH), 7.85-7.77 (m, 3H, ArH), 7.48 (d, J = 9.0 Hz, 1H, ArH), 7.44 (d, J = 9.0 Hz, 1H, ArH), 7.31-7.03 (m, 10H, ArH), 6.61-6.60 (m, 2H, ArH), 6.51-6.50 (m, 2H, ArH), 5.66 (s, 1H, ArOH), 4.59-4.37 (m, 5H, ArCH

2

Ar, ArOCH

2

C(O)), 4.24-3.98 (m, 10H, OCH

2

O, ArCH

2

Ar), 3.82-3.61 (m, 9H, OCH

₂

O, ArCH

₂

Ar), 3.28-3.13 (m, 4H, ArCH

₂

Ar, C(O)CH

₂

₃

), 1.33 (s, 9H, ArC(CH

3

)

3

), 1.31 (s, 9H, ArC(CH

3

)

3

), 1.23 (t, J = 7.2 Hz, 3H, C(O)CH

2

3

), 0.88 (s, 9H, ArC(CH

3

)

3

), 0.82 (s, 9H, ArC(CH

3

)

3

);

13

C-NMR (75.4 MHz, CDCl

3

) δ 169.56 (C

q

), 154.67 (C

q

), 154.08 (C

q

), 153.47 (C

_q

), 152.02 (C

_q

), 150.92 (C

_q

), 150.35 (C

_q

), 145.68 (C

_q

), 145.53 (C

q

), 141.42 (C

q

), 135.62 (C

q

), 135.58 (C

q

), 134.13 (C

q

), 133.98 (C

q

), 132.86 (C

q

), 131.95 (C

q

), 131.77 (C

q

), 131.73 (C

q

), 129.45 (C

q

), 129.18 (CH), 128.97 (C

q

), 128.69 (C

q

), 127.79 (CH), 126.22 (CH), 126.01 (CH), 125.71 (CH), 125.51 (CH), 125.41 (CH), 125.36 (CH), 125.09 (CH), 125.05 (CH), 124.92 (CH), 123.43 (CH), 123.28 (CH), 120.56 (C

_q

), 119.63 (C

q

), 116.74 (CH), 114.39 (CH), 74.91 (CH

2

), 72.22 (CH

2

), 71.38 (CH

2

), 70.06 (CH

2

), 69.79 (CH

2

), 69.40 (CH

2

), 69.24 (CH

2

), 69.15 (CH

2

), 68.26 (CH

2

), 60.90 (CH

2

), 34.07 (C

q

), 33.78 (C

q

), 33.69 (C

q

), 33.60 (C

q

), 31.68 (CH

₃

), 31.62 (CH

₃

), 31.45 (CH

₂

), 31.29 (CH

₂

), 31.11 (CH

₂

), 31.01 (CH

3

), 30.97 (CH

3

), 30.86 (CH

2

), 14.14 (CH

3

); mp 140-143

^o

C; [α]

D

25

= -60.0 (c = 0.005, CHCl

3

). FAB-MS: m/z (%) 1184 (M + Na

⁺

, 82), 1161 (M

⁺

, 57), 612 (100), 596 (60).

148

General Procedure for the Synthesis of (S)-(-)-49a and (S)-(-)-49b.

OHO O O

O O

(S)-(-)-48a

OHO O O

O O

HO O

(S)-(-)-49a

THF/H₂O (v/v = 2/1), 18 h NaOH

O O O

O O

(S)-(-)-48b

O O O

O O

HO O

(S)-(-)-49b

THF/H₂O (v/v = 2/1), 18 h NaOH

A mixture of compound (S)-(-)-48a or (S)-(-)-48b ((S)-(-)-48a: 0.10 g, 0.12 mmol; (S)-(-)-48b: 0.10 g, 0.12 mmol) and sodium hydroxide (150 mg, 3.75 mmol) in THF and water (v/v = 2/1,48 mL) was stirred vigorously and heated at reflux for 18 h. The solvent was removed under reduced pressure, and the crude in water was partitioned between 10%

HCl (50 mL) and CH

₂

. The organic layer was dried over anhydrous MgSO

4

. The crude material was purified over silica gel column elutiong with hexane/acetone (v/v = 1/3) containing increasing amounts of CH

3

OH from 0 to 50%) to give the compound (S)-(-)-49a or (S)-(-)-49b ((S)-(-)-49a: 87 mg, 90%; (S)-(-)-49b 88 mg, 91%) s a white solid.

149

Data for (S)-(-)-49a: R

f

= 0.48 (silica, hexane/ethyl acetate = 1/1)

¹

H NMR (CDCl

3

, 300MHz) δ

H

7.77-7.67 (m, 3H, ArH), 7.48-7.47 (m, 1H, ArH), 7.40 (d, J = 8.9 Hz, 1H, ArH), 7.29-6.91 (m, 10H, ArH), 6.81 (d, J

= 8.7 Hz, 1H, ArH), 6.67 (d, J = 8.7 Hz, 1H, ArH), 6.60 (s, 1H, ArH), 6.54 (s, 1H, ArH), 6.36 (s, 1H, ArH), 6.19 (s, 1H, ArH), 4.84 (d, J = 12.0 Hz, 1H, ArCh

2

A), 4.69 (d, J = 12.6 Hz, 1H, ArCh

2

A), 4.51-4.15 (m, 7H, ArCh

2

A, OCH

2

C(O), OCH

2

O), 3.97-3.85 (m, 2H, ArCh

2

A, OCH

₂

O), 3.68-3.34 (m, 7H, ArCh

₂

A, OCH

₂

O), 3.15-2.73 (m, 7H, ArCh

2

A, OCH

2

O), 2.07 (d, J = 12.6 Hz, 1H, ArCh

2

A), 1.96 (d, J = 11.7 Hz, 1H, ArCh

2

A), 1.23 (s, 9H, ArCCH

3

), 1.14 (s, 9H, ArCCH

3

), 1.00 (s, 9H, ArCCH

3

), 0.66 (s, 9H, ArC(CH

3

)

3

);

¹³

C-NMR (75.4 MHz, CDCl

3

) δ 173.4 (C

_q

), 155.95, (C

_q

), 154.99 (C

_q

), 154.48 (C

_q

), 154.03 (C

_q

), 152.85 (C

_q

), 150.15 (C

_q

), 149.48 (C

_q

), 149.02 (C

_q

), 147.86 (C

_q

), 147.43 (C

_q

), 146.76 (C

q

), 144.90 (C

q

), 142.90 (C

q

), 142.49 (C

q

), 135.29 (C

q

), 134.54 (C

q

), 134.26 (C

q

), 134.14 (C

q

), 133.35 (C

q

), 132.81 (C

q

),132.31 (C

q

), 131.92 (C

q

), 130.42 (CH), 129.21 (CH), 128.20 (CH), 128.08 (CH), 127.87 (CH), 126.89 (CH), 126.67 (CH), 126.34 (CH), 126.09 (CH), 125.81 (CH), 125.62 (CH), 125.43 (CH), 124.92 (CH), 124.69 (CH), 124.43 (CH), 124.92 (CH), 123.98 (CH), 123.36 (CH), 118.43 (CH), 114.88 (C

q

), 113.83 (C

q

), 76.27 (CH

2

), 75.80 (CH

2

), 74.75 (CH

2

), 73.91 (CH

₂

), 71.10 (CH

₂

), 70.84 (CH

₂

), 70.51 (CH

₂

), 70.35 (CH

₂

), 70.07 (CH

₂

), 69.21 (CH

₂

), 68.93 (CH

₂

), 34.53 (C

_q

), 34.33 (C

_q

), 34.01 (C

_q

), 33.89 (C

_q

), 32.91 (CH

2

), 32.48 (CH

2

), 32.01 (CH

3

), 31.77 (CH

3

), 31.72 (CH

3

), 31.54 (CH

3

), 30.73 (CH

2

), 30.13 (CH

2

); mp 210-212

^o

C; [α]

D

25

= -61.0 (c = 0.005, CHCl

3

). FAB-MS: m/z (%) 1156 (M + Na

⁺

, 12), 313 (73), 307 (100).

150

Data for (S)-(-)-49b: R

f

= 0.37 (silica, hexane/ethyl acetate = 1/1)

¹

H NMR (CDCl

3

, 300MHz) δ

H

7.83-7.70(m, 4H, ArH), 7.31-6.91 (m, 16H, ArH), 4.89-4.57 (m, 4H, ArCh

2

A, OCH

2

C(O)), 4.36-3.11 (m, 24H, ArCh

₂

A, OCH

₂

C(O), OCH

₂

O), 1.18 (s, 9H, ArCCH

₃

), 1.13 (s, 9H, ArCCH

3

), 1.08 (s, 9H, ArCCH

3

), 1.03 (s, 9H, ArC(CH

3

)

3

);

¹³

C-NMR (75.4 MHz, CDCl

3

) δ 154.95 (C

_q

), 154.16 (C

q

), 153.15 (C

q

), 150.01 (C

q

), 149.58 (C

q

), 146.42 (C

q

), 145.80 (C

q

), 145.89 (C

q

), 135.39 (C

q

), 134.81 (C

_q

), 134.05 (C

_q

), 133.95 (C

_q

), 133.12 (C

_q

), 131.99 (C

_q

), 131.70 (C

_q

), 129.52 (CH), 129.06 (CH), 128.99 (CH), 127.92 (CH), 127.71 (CH), 126.26 (CH), 126.09 (CH), 125.79 (CH), 125.60 (CH), 125.44 (CH), 125.22 (CH), 125.10 (CH), 124.92 (CH), 123.61 (CH), 123.28 (CH), 121.22 (C

_q

), 119.27 (C

_q

), 114.34 (CH), 74.86 (CH

₂

), 69.77 (CH

₂

), 69.22 (CH

₂

), 68.63 (CH

₂

), 34.06 (C

_q

), 33.83 (Cq), 33.73 (C

_q

), 33.65 (C

_q

), 31.94 (CH

2

), 31.88 (CH

2

), 31.63 (CH

3

), 31.60 (CH

3

), 31.05 (CH

3

), 30.99 (CH

3

), 29.65 (CH

2

), 29.32 (CH

2

); mp 208-210

^o

C; [α]

D

25

= -62.0 (c = 0.005, CHCl

3

). FAB-MS: m/z (%) 1194 (M + Na

⁺

+ K

⁺

, 13), 1178 (M + 2Na

⁺

, 38), 1156 (M + Na

⁺

, 100), 623 (54).

151

在文檔中芳杯冠醚修飾聯二萘酚衍生物之合成與其對胺基醇之掌性辨識研究 (頁 158-184)

第五章 實驗部份

5.2 實驗步驟及光譜資料

53

rac-1 83%

3

2

o

3

3

4

1

3

H

13

3

o

54a

36a n = 1 97%

36b n = 2 96%

35a n = 1 97%

35b n = 2 96%

126

2

4

1

3

H

2

2

2

2

2

2

2

2

13

3

2

2

2

2

1

3

H

13

3

2

2

2

2

2

2

rac-37b. 54a

(S)-(-)-37a n = 1 80%

(S)-(-)-37b n = 2 85%

rac-37b n = 2, 90%

rac-1 (S)-(-)-1

36a n = 1

36b n = 2

127

2

3

2

1

3

H

2

2

2

2

2

2

2

2

2

13

3

q

q

第五章實驗部份

⁵³

₃

^o

₃

¹

₃

_H

¹³

^o

^54a

₂

¹

₂

₂

₂

₂

¹³

₂

¹

₃

_H

¹³

₂

₂

₂

₂

₂

rac-37b. ^54a

₂

¹

_H

₂

₂

₂

₂

₃

⁺

⁺

¹

¹³

_q

_q

⁺

⁺

⁵⁴

¹

₃

_H

₂

₂

₂

₂

¹³

₂

₂

₂

₂

₃

⁺

¹