Synthesis of Compound 2c

At room temperature, to a suspension of NaH (1.18 g, 18.6 mmol) in THF (10 mL) was added dropwise to a THF solution (30 mL) of 2,2-dimethyl-1,3-propandiol (2.79 g, 26.8 mmol) with stirring for 30 min, and the resulting mixture was then heated to reflux for 1h. After cooling to room temperature, to this solution was added (2-Bromoethylidene)cyclopentane (3.5 ml, 29.5 mmol) slowly in 1 h, and the mixture

37

was refluxed for 8 h. The resulting solution was treated with water and extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate and concentrated under reduced pressure to afford crude product 2b-1 (3.18 g, 60 %) that was purified by chromatography through a silica column (hexane/EA: 4/1).

Spectroscopic data of 2b-1:

¹

H NMR (δ, CDCl

3

): 5.38 (m, 1H, HC=); 3.91 (m, 2H, OCH

2

); 3.47 (s, 1H, OH); 3.41 (d, 2H,

² J HH

= 5.84 Hz, OCH

2

); 3.25 (s, 2H, OCH

2

); 2.22, 1.62 (m, 8H, 4 CH

2

); 0.89 (s, 6H, 2 CH

3 ¹³

C NMR (δ, CDCl

3

): 139.70 (=C); 119.77 (HC=); 77.52, 72.15, 69.27 (3 OCH

2

); 39.58 (C); 33.49, 26.10, 25.82 (4 CH

2

); 22.57 (2 CH

3

). MS (ESI

⁺

) m/z: 221.1652 (M+Na)

⁺

Compound 2b-1 (3.18 g, 16.1 mmol) was dissolved in CH

2

(50 mL) and to this solution was slowly added PCC/celite (1:1 w/w, 6.91 g, 32.1 mmol). The resulting mixture was stirred for 3 h, and the resulting solution was diluted with hexane (50 mL)

and purified by flash column to give 2b-2 (2.99 g, 95 %.) Spectroscopic data of 2b-2:

1

H NMR (δ, CDCl

3

): 9.53 (s, 1H, CHO); 5.36 (m, 1H, HC=); 3.90 (m, 2H, OCH

2

): 3.38

(s, 2H, OCH

2

); 2.22, 1.61 (m, 8H, 4 CH

2

); 1.05 (s, 6H, 2 CH

3 ¹³

C NMR (δ, CDCl

3

206.42 (CHO); 142.36 (=C); 123.54 (HC=); 77.52, 68.15 (2 OCH

2

); 42.13 (C); 33.49, 28.62, 25.82 (4 CH

2

); 18.62 (2 CH

3

). MS (ESI

⁺

) m/z: 219.1562 (M+Na)

⁺

To a solution of compound 2b-2 (2.99 g, 15.2 mmol) in THF (30 mL), was added ethynylmagnesium bromide (38.4 ml, 19.2 mmol) at room temperature and under

38

nitrogen. The solution was stirred for 14h. After quenching by aqueous NH

4

Cl solution (30 mL), the solution was extracted with ether (3x20 mL), then dried over sodium sulfate and concentrated under reduced pressure and eluted through a silica column (hexane/EA: 4/1) to give compound 2b (3.04 g, 90 % yields). Spectroscopic data of 2b:

1

H NMR (δ, CDCl

3

): 5.36-5.42 (m, 1H, HC=); 4.15 (dd, 1H,

³ J HH

= 7.10 Hz,

⁴ J HH

2.00 Hz, CH); 3.93 (m, 2H, OCH

2

); 3.74 (d, 1H,

³ J HH

= 7.10 Hz, OH); 3.58, 3.21 (2d, 2H,

² J HH

= 9.09 Hz, OCH

2

); 4.15 (d, 1H,

⁴ J HH

= 2.00 Hz, ≡CH); 2.22 (dt, 4H,

³ J HH

= 19.12 Hz,

⁴ J HH

= 6.67 Hz, 2 CH

2

); 1.63 (m, 4H, 2 CH

2 ¹³

C NMR (δ, CDCl

3

): 148.40 (=C); 115.97 (HC=); 83.33 (≡C); 77.52, 69.27 (2 OCH

2

); 73.13 (≡CH); 70.25 (CH);

38.58 (C); 33.49, 28.63, 26.10, 25.82 (4 CH

2

); 21.92, 20.70 (2 CH

3

). MS (ESI

⁺

) m/z:

245.1508 (M+Na)

⁺

Synthesis of Complex 3. A mixture of [Ru]Cl (250 mg, 0.34 mmol), 1 (61 mg, 0.34

mmol), and NH

4

6

(81 mg, 0.50 mmol), in CH

2

(20 mL) was stirred at ambient temperature for one day. The resulting brown solution was filtered through a bed of Celite to remove the insoluble salts, and the pad was eluted with CH

2

until the eluent was colorless, then the solvent of the filtrate were removed under vacuum and the solid

39

residue was extracted with a small volume of CH

2

followed by re-precipitation by a 50 mL of stirred diethyl ether. Precipitates thus formed were collected in a glass frit, washed with diethyl ether/hexane 1:1 and dried under vacuum. The final product can be obtained as a light orange powder identified as 3 (210 mg, 70% yields). Spectroscopic data of 3:

¹

H NMR (δ, CDCl

3

): 6.94-7.66 (m, 34H, Ph); 5.13 (s, 5H, Cp); 4.57 (d, 1H,

³ J HH

= 10.47 Hz, CβH); 4.76, 4.54 (s, 2H, =CH

2

); 4.12 (t, 2H,

³ J HH

=15.11 Hz, CH

2

);

3.30, 3.16 (2d, 2H,

² J HH

=12.71 Hz, CH

2

); 2.35, 2.15 (m, 2H, CH

2

); 0.99, 0.97 (s, 6H, 2CH

3 ¹³

C NMR (δ, CDCl

3

): 343.94 (t,

³ J CP

=15.21 Hz, Cα); 147.04 (C=);

128.21-134.61 (Ph); 115.64 (Cβ); 112.92 (CH

2

=); 94.32 (Cp); 76.80, 74.43, 38.69 (3 CH

2

); 44.23 (CH); 38.16, 26.09 (2 CH

3

); 21.90 (CH

3 ³¹

P NMR (δ, CDCl

3

): 43.24, 43.02 (2d,

² J PP

=26.35 Hz, PPh

3

). MS (ESI

⁺

) m/z: 855.2453 (M)

⁺

Synthesis of Complex 4. The mixture of 3 (85 mg, 0.099 mmol) and NaOMe (6.0 mg,

0.11 mmol) in MeOH (30 mL) was stirred for 5 m at room temperature. After that, solvent of the solution was removed under vacuum and then 20 mL of diethyl ether was added and the mixture was stirred using an ultrasonic cleaner. The solution was filtered through neutral Al

2

3

to remove the insoluble salts, and then solvent of the filtrate was removed under vacuum. The final product can be obtained as a yellow solid identified

40

as 4 (77 mg, 90% yield). Spectroscopic data of 4:

¹

H NMR (δ, C

6

): 7.69-7.73 (m, 12H, Ph); 6.92-6.98 (m, 18H, Ph); 5.00, 4.79 (s, 2H, =CH

2

); 4.39 (s, 5H, Cp); 4.59, 4.26 (2d, 2H,

² J HH

=14.17 Hz, OCH

2

); 3.90, 3.33 (2d, 2H,

² J HH

=11.81 Hz, OCH

2

); 2.86 (m, 2H, CH

2

); 2.76 (m, 1H, CγH); 1.51 (s, 3H, CH

3

); 1.22 (s, 3H, CH

3 ¹³

C NMR (δ, C

6

127.39-140.12 (Ph); 113.45 (Cβ); 92.69 (t,

² J CP

=24.43 Hz, Cα); 85.44 (Cp); 110.72 (CH

2

=), 151.45 (C=); 78.96, 75.42, 39.64 (3 CH

2

); 26.63, 21.74 (2 CH

3

); 39.59 (C).

³¹

P NMR (δ, C

6

): 51.94 (s, PPh

3

). MS (ESI

⁺

) m/z: 855.2469 (M+1)

⁺

Synthesis of Complex 5a. Complex 4 (110 mg, 0.13 mmol) and KPF 6

(26 mg, 0.14 mmol) were added into a Schlenk flask, and CH

2

(20 mL) was added under nitrogen atmosphere. Allyl bromide (17 mg, 0.14 mmol) was added to the resulting solution which was stirred for 8 h. After that, the solution was filtered through a bed of Celite to remove the insoluble salts, then the solvent of the filtrate was removed under vacuum and the solid residue was extracted with a small volume of CH

2

followed by re-precipitation by adding to a 50 mL of stirred ethyl ether. Precipitates thus formed were collected in a glass frit, washed with ethyl ether/hexane 1:1 and dried under

41

vacuum. The final product was obtained as a deep yellow powder identified as 5a (100 mg, 90% yield). Spectroscopic data of 5a:

¹

H NMR (δ, CDCl

3

): 7.74-6.79 (m, 49H, Ph);

5.89 (m, 1H, =C(C)H); 5.11 (s, 5H, Cp); 5.11 (m, 2H, =CH

2

); 4.63, 4.55 (s, 2H, =CH

2

);

4.16, 3.75 (2d, 2H,

² J HH

=14.25 Hz, OCH

2

); 3.26, 2.72 (2d, 2H,

² J HH

=12.21 Hz, OCH

2

);

3.13, 2.77 (dd, 2H,

² J HH

=16.79 Hz,

³ J HH

=6.11 Hz, CH

2

); 2.65, 2.25 (m, 2H, CH

2

); 2.22

(d,

³ J HH

=6.11 Hz, 1H, CH) 1.04, 0.83 (s, 6H, 2CH

3 ¹³

C NMR (δ, CDCl

3

): 349.67 (t,

3 J CP

=14.04 Hz, Cα); 148.16-111.99 (Cβ, Ph, =C(CH

2

)

2

, =CH

2

); 94.02 (Cp); 81.98

(OCH

2

); 74.50 (OCH

2

); 4.77 (CH); 39.97 (CH

2

); 38.33 (C); 27.56 (CH

2

); 26.46 (CH

3

);

21.00 (CH

3 ³¹

P NMR (δ, CDCl

3

): 41.38, 40.68 (2d,

² J PP

=27.68 Hz, PPh

3

). MS (ESI

⁺

) m/z: 895.2813 (M)

⁺

Synthesis of Complex 5b. Complex 5b (120 mg, 93% yield) was similarly prepared

from 4 (130 mg, 0.15 mmol), KPF

6

(31 mg, 0.18 mmol) and methyl iodide (26 mg, 0.18 mmol). Spectroscopic data of 5b:

¹

H NMR (δ, CDCl

3

):7.77-6.93 (m, 42H, Ph); 5.14 (s, 5H, Cp); 4.63, 4.41 (s, 2H, =CH

2

); 4.18, 3.87 (2d, 2H,

² J HH

=14.18 Hz, OCH

2

); 3.34, 2.92 (2d, 2H,

² J HH

=12.02 Hz, OCH

2

); 2.49 (t, 1H,

³ J HH

=12.91 Hz, CH); 2.20, 1.86 (2d, 2H,

² J HH

=11.57 Hz, CH

2

); 1.76, 1.04, 0.93 (s, 9H, 3CH

3 ¹³

C NMR (δ, CDCl

3

): 350.81

42

(t,

³ J CP

=15.19 Hz, Cα); 148.22 (=C(CH

2

)

2

); 135.23-128.42 (Cβ, Ph); 112.23 (=CH

2

);

93.93 (Cp); 81.00 (OCH

2

); 74.59 (OCH

2

); 43.85 (CH

2

); 40.15 (CH

2

); 36.34 (C); 27.12 (CH

3

); 21.65 (CH

3

); 7.98 (CH

3 ³¹

P NMR (δ, CDCl

3

): 42.43, 41.44 (2d,

² J PP

=26.42 Hz, PPh

3

). MS (ESI

⁺

) m/z: 869.2641 (M)

⁺

Synthesis of Compound 6. The solution of complex 3 (150 mg, 0.17 mmol) in CDCl 3

(1.5 mL) and CH

3

CN (121 mg, 3.0 mmol, 0.15 mL) in an NMR tube was heated at 60

^o

C for 24 h. Then CDCl

3

and CH

3

CN were removed in vacuo and CH

2

(1.0 mL) was used to extract the product and diethyl ether (6.0 mL) was then added. The pale-orange precipitates thus formed was filtered and washed with diethyl ether and dried under vacuum to give [Ru]NCCH

3 +

. The filtrate was evaporated to dryness under vacuum and the crude product purified by flash chromatography (silica gel, hexanes/EtOAc = 10/1) to afford 6 (26 mg, 92%). Spectroscopic data for 6:

¹

H NMR (δ, CDCl

3

): 4.92, 4.83 (s, 2H, =CH

2

); 4.23, 4.13 (2d, 2H,

² J HH

=14.51 Hz, OCH

2

); 3.35, 3.13 (2d, 2H,

² J HH

=12.51 Hz, OCH

2

); 2.48 (m, 2H, CH

2

); 2.23 (dt, 1H,

³ J HH

=9.54 Hz,

⁴ J HH

= 2.50 Hz, CH); 2.10 (d, 1H,

⁴ J HH

=2.50 Hz, HC≡); 1.03, 0.94 (s, 6H, 2CH

3 ¹³

C NMR (δ, CDCl

3

): 147.49 (=C); 112.67 (H

2

C=); 85.72 (≡C); 77.28, 74.59, 36.23 (3CH

2

); 70.97 (HC≡); 34.21 (≡C);

43

37.74 (C); 25.31, 20.92 (3 CH

3

). MS (ESI

⁺

) m/z: 165.1217(M+1).

Synthesis of Compound 7a. The solution of 1 (65 mg, 0.36 mmol) and [Ru]NCCH 3 +

(78 mg, 0.11 mmol) in a 2:1 cosolvent of CHCl

3

/MeOH was heated to 50

^o

C for 1 day.

Then the solvent was removed under vacuum and 1 mL of CH

2

was used to extract the crude product. This is followed by re-precipitation by a 10 mL of stirred diethyl ether. The pale-orange precipitates thus formed were filtered and washed with diethyl ether and dried under vacuum to give [Ru]NCCH

3 +

. The filtrate was evaporated to dryness under vacuum and the crude product purified by flash chromatography (silica

gel, hexanes/EtOAc = 10/1) to afford 7a (55 mg, 77%). Spectroscopic data for 7a:

¹

H NMR (δ, CDCl

3

): 5.81 (m, 1H, =C(C)H); 5.70 (m, 1H, =C(C)H); 4.12, 3.19 (2d, 2H,

2 J HH

=14.07 Hz, OCH

2

); 3.44, 3.11 (2d, 2H,

² J HH

=12.27 Hz, OCH

2

); 3.28 (s, 3H, OCH

3

);

2.62 (2d, 1H,

² J HH

=12.82 Hz, CH

2

); 2.12, 1.92 (m, 2H, CH

2

); 2.05 (br, 1H, CH); 1.43 (dd, 1H,

² J HH

=12.82 Hz,

³ J HH

=7.31 Hz, CH

2

); 1.14, 0.81 (s, 6H, 2CH

3 ¹³

C NMR (δ, CDCl

3

): 128.96, 126.25 (2C=); 83.09, 81.60 (2OCH

2

); 78.42 (C); 49.29 (OCH

3

); 44.46 (CH); 38.01 (C); 36.57, 28.91 (2CH

2

); 26.67, 23.75 (2CH

3

). MS (ESI

⁺

) m/z: 197.8102

44

(M+H)

⁺

Synthesis of Compound 7b. Compound 7b (49 mg, 70% yield) was similarly prepared

from 1 (61 mg, 0.33 mmol), [Ru]NCCH

3 +

(73 mg, 0.10 mmol) in a 2:1 cosolvent of

CHCl

3

/EtOH, and the solution was heated to 50

^o

C for 1 day. Spectroscopic data of 7b:

1

H NMR (δ, CDCl

3

): 5.80 (m, 1H, =C(C)H); 5.70 (m, 1H, =C(C)H); 4.11, 3.22 (2d, 2H,

2 J HH

=13.96 Hz, OCH

2

); 3.53 (m, 2H, OCH

2

); 3.43, 3.11 (2d,

² J HH

=12.16 Hz, 2H, OCH

2

);

2.61 (d, 1H,

² J HH

=12.77 Hz, CH

2

); 2.14, 1.93 (m, 2H, CH

2

); 2.04 (br, 1H, CH); 1.47 (dd, 1H,

² J HH

=13.30 Hz,

³ J HH

=7.48 Hz, CH

2

); 1.15 (t, 3H,

³ J HH

=7.06 Hz, CH

3

); 1.13 (s, 3H, CH

3

); 0.81 (s, 3H, CH

3 ¹³

C NMR (δ, CDCl

3

): 128.94, 126.34 (2C=); 83.08, 81.60 (2 OCH

2

); 78.42 (C); 49.29 (OCH

3

); 44.46 (CH); 38.01 (C); 36.57, 28.91 (2 CH

2

); 26.67, 23.75 (2 CH

3

). MS (ESI

⁺

) m/z: 211.8102 (M+H)

⁺

Synthesis of Compound 7c. Compound 7c (30 mg, 43% yield) was similarly prepared

from 1 (57 mg, 0.31 mmol), [Ru]NCCH

3 +

(68 mg, 0.093 mmol) in a 2:1 cosolvent of

CHCl

3

/i-PrOH, and the solution was heated to 50

^o

C for 1 day. Spectroscopic data of 7c:

1

H NMR (δ, CDCl

3

): 5.78 (m, 1H, =C(C)H); 5.68 (m, 1H, =C(C)H); 4.11, 3.23 (2d, 2H,

2 J HH

=13.95 Hz, OCH

2

); 3.94 (Septet, 1H,

³ J HH

=6.18 Hz, CH); 3.44, 3.12 (2d, 2H,

2 J HH

=12.12 Hz, OCH

2

); 2.58 (d, 1H,

² J HH

=12.68 Hz, CH

2

); 2.12, 1.91 (m, 2H, CH

2

);

2.03 (br, 1H, CH); 1.51 (dd, 1H,

² J HH

=12.51 Hz,

³ J HH

=7.33 Hz, CH

2

); 1.14(s, 3H,

45

3

);0.81 (s, 3H, CH

3

); 1.13 (s, 6H, 2 CH

3 ¹³

C NMR (δ, CDCl

3

): 128.86, 126.38 (2C=); 83.16, 83.07 (2 OCH

2

); 79.03 (C); 64.23 (OCH); 44.53 (CH); 37.98 (C); 37.64, 31.07 (2 CH

2

); 26.70, 25.54, 25.33, 23.76 (4 CH

3

). MS (ESI

⁺

) m/z: 247.1661 (M+Na)

⁺

Synthesis of Complex 8. A mixture of [Ru]Cl (148 mg, 0.21 mmol), 2a (50 mg, 0.25

mmol), and NH

4

6

(85 mg, 0.32 mmol), in CH

2

(20 mL) was stirred at ambient temperature for one day. The resulting brown solution was filtered through a bed of Celite to remove the insoluble salts, and the pad was eluted with CH

2

until the eluent was colorless, then the solvent of the filtrate were removed under vacuum and the solid residue was extracted with a small volume of CH

2

followed by re-precipitation by a 50 mL of stirred diethyl ether. Precipitates thus formed were collected in a glass frit, washed with diethyl ether/hexane 1:1 and dried under vacuum. The final product can be obtained as a deep yellow powder identified as 8 (147 mg, 68% yields).

The ratio of anti- and syn- isomers is 1:0.5.

Spectroscopic data for the anti-isomers:

¹

H NMR (δ, CD

2

): 7.93- 6.99 (m, 70H, Ph);

5.12 (s, 5H, Cp); 5.10, 4.89 (s, 2H, 2 HC=); 4.23 (dt, 1H,

³ J HH

=9.78 Hz,

⁴ J HP

=2.69 Hz, CβH); 3.92 (dd, 1H,

² J HH

=11.38 Hz,

³ J HH

=4.36 Hz, OCH

2

); 3.58 (2d, 1H,

² J HH

=11.09

46

Hz, OCH

2

); 3.27 (m, 1H, OCH

2

); 3.12 (2d, 1H,

² J HH

=11.45 Hz, OCH

2

); 2.67 (dd, 1H,

3 J HH

=9.78 Hz,

³ J HH

=11.20 Hz, CH); 2.18 (dt, 1H,

³ J HH

=11.20 Hz,

³ J HH

=4.36 Hz, CH);

1.73, 0.97, 0.82 (s, 9H, 3CH

3 ¹³

C NMR (δ, CD

2

): 343.71 (t,

² J CP

=14.86 Hz, Cα);

145.33 (=C); 135.38-128.27 (Ph); 114.31 (Cβ ); 113.07 (CH

2

=); 94.70 (Cp); 78.73, 72.34 (2 OCH

2

); 47.55, 45.66 (2 CH); 35.27 (C); 25.97, 22.72, 19.34 (3 CH

3 ³¹

P NMR (δ, CD

2

): 43.75, 43.12 (2d,

² J PP

=26.49 Hz, PPh

3

). MS (ESI

⁺

) m/z: 869.2624 (M)

⁺

. Spectroscopic data for the syn-isomer:

¹

H NMR (δ, CD

2

): 7.93- 6.99 (m, 70H, Ph);

5.12 (s, 5H, Cp); 5.10, 4.68 (s, 2H, 2 HC=); 4.44 (d, 1H,

³ J HH

=10.46 Hz, CβH); 3.80 (dd, 1H,

² J HH

=11.87 Hz,

³ J HH

=3.39 Hz, OCH

2

); 3.43 (t, 1H,

² J HH

=11.87 Hz, OCH

2

); 3.25 (m,

1H, OCH

2

); 3.09 (2d, 1H,

² J HH

=11.97 Hz, OCH

2

); 2.96 (dd, 1H,

³ J HH

=10.46 Hz,

3 J HH

=3.55 Hz, CH); 2.79 (br, 1H, CH); 1.80, 1.21, 0.86 (s, 9H, 3CH

3 ¹³

C NMR (δ,

2

): 342.67 (t,

² J CP

=15.08 Hz, Cα); 145.26 (=C); 135.38-128.27 (Ph); 111.24 (Cβ );

111.01 (CH

2

=); 94.61 (Cp); 72.54, 65.93 (2 OCH

2

); 43.06, 42.18 (2 CH); 34.38 (C);

26.26, 24.39, 23.21 (3 CH

3 ³¹

P NMR (δ, CD

2

): 45.22, 43.50 (2d,

² J PP

=26.79 Hz, PPh

3

). MS (ESI

⁺

) m/z: 869.2624 (M)

⁺

Synthesis of Complex 9. The mixture of 8 (75 mg, 0.086 mmol) and NaOMe (6 mg,

47

2

3

to remove the insoluble salts, and then solvent of the filtrate was removed under vacuum. The yellow final product can be obtained and was identified as

9 (67 mg, 90% yield). Spectroscopic data of 9:

The ratio of anti- and syn- isomers is 1:0.5.

Spectroscopic data for the anti-isomer:

¹

H NMR (δ, C

6

): 7.56-7.65 (m, 20H, Ph);

6.95-6.96 (m, 30H, Ph); 4.96, 4.93 (s, 2H, =CH

2

); 4.40 (s, 5H, Cp); 4.11,3.35 (dd, 2H,

2 J HH

=11.37 Hz,

³ J HH

=4.60, OCH

2

); 3.70, 3.16 (2d, 2H,

² J HH

=10.79 Hz, OCH

2

); 2.81 (m,

1H, CH); 2.69 (d, 1H,

³ J HH

=11.36 Hz, CH); 1.79 (s, 3H,CH

3

); 1.43 (s, 3H, CH

3

); 1.07 (s,

3H, CH

3 ¹³

C NMR (δ, C

6

): 146.24 (=C); 127.50-140.52 (Ph); 112.72 (=CH

2

);

110.58 (Cβ); 92.19 (t,

² J CP

=24.98 Hz, Cα); 85.69 (Cp); 79.07 (OCH

2

); 73.46 (OCH

2

);

48.72 (CH); 46.15 (CH); 35.64 (C); 26.334, 20.93, 20.71 (3CH

3 ³¹

P NMR (δ, C

6

51.22 (s, PPh

3

). MS (ESI

⁺

) m/z: 869.2634 (M+1)

⁺

Spectroscopic data for the syn-isomer:

¹

H NMR (δ, C

6

): 7.56-7.65 (m, 20H, Ph);

6.95-6.96 (m, 30H, Ph); 4.93, 4.66 (s, 2H, =CH

2

); 4.41 (s, 5H, Cp); 4.37,4.28 (dd, 2H,

2 J HH

=10.60 Hz,

³ J HH

=3.34 Hz, OCH

2

); 4.03, 3.41 (2d, 2H,

² J HH

=10.78 Hz, OCH

2

); 3.05

(br, 1H, CH); 2.81 (m, 1H, CH); 1.91 (s, 3H,CH

3

); 1.29 (s, 3H, CH

3

); 1.01 (s, 3H, CH

3

48

13

C NMR (δ, C

6

): 146.69 (=C); 127.50-140.52 (Ph); 109.13 (H

2

C=); 108.51 (Cβ);

93.83 (t,

² J CP

=24.98 Hz, Cα); 85.69 (Cp); 74.07 (OCH

2

); 67.76 (OCH

2

); 44.81 (CH);

42.57 (CH); 35.22 (C); 26.74, 25.61, 22.61 (3CH

3 ³¹

P NMR (δ, C

6

): 52.16, 50.34 (2d,

² J PP

=37.98 Hz, PPh

3

). MS (ESI

⁺

) m/z: 869.2634 (M+1)

⁺

Synthesis of Complex 10. Complex 9 (165 mg, 0.19 mmol) and KPF 6

(39 mg, 0.21 mmol) were added into a Schlenk flask, and CH

2

(20 mL) was added under nitrogen atmosphere. Allyl bromide (26 mg, 0.21 mmol) was added to the resulting solution which was stirred for 8 h. After that, the solution was filtered through a bed of Celite to remove the insoluble salts, then the solvent of the filtrate was removed under vacuum and the solid residue was extracted with a small volume of CH

2

followed by re-precipitation by adding to a 50 mL of stirred ethyl ether. Precipitates thus formed were collected in a glass frit, washed with ethyl ether/hexane 1:1 and dried under vacuum. The final product was obtained as a light pink powder identified as 10 (160 mg, 93% yield). Spectroscopic data of 10:

The ratio of anti- and syn- isomers is 1:0.3.

49

Spectroscopic data for the anti-isomer:

¹

H NMR (δ, CDCl

3

): 6.68-7.75 (m, 50H, Ph);

6.09 (m, 1H, =C(C)H); 5.13 (s, 5H, Cp); 5.28-4.91 (m, 4H, 2 =CH

2

); 3.90,2.86 (2d, 2H,

2 J HH

=10.29 Hz, OCH

2

); 3.27, 2.69 (2d, 2H,

² J HH

=10.85 Hz, OCH

2

); 2.44 (br, 2H, 2 CH);

1.81, 1.10, 0.63 (s, 9H, 3 CH

3 ¹³

C NMR (δ, CDCl

3

): 349.91 (t,

³ J CP

=12.18 Hz, Cα);

144.24 (=C); 139.19(=C(C)H); 122.36-135.13 (Ph, Cβ, =C); 116.54, 113.72 (2 =CH

2

);

94.36 (Cp); 80.60, 73.89 (2 OCH

2

); 42.91, 42.85 (2 CH); 36.73 (C); 28.43 (CH

2

); 26.46, 23.57, 22.11 (3 CH

3 ³¹

P NMR (δ, CDCl

3

): 40.56 (br, PPh

3

). MS (ESI

⁺

) m/z: 909.2948 (M)

⁺

Spectroscopic data for the syn-isomer:

¹

H NMR (δ, CDCl

3

): 6.68-7.75 (m, 50H, Ph);

5.95 (m, 1H, =C(C)H);5.38, 5.04 (m, 4H, 2 =CH

2

); 5.17 (s, 5H, Cp); 3.79-3.04 (m, 6H, CH

2

, 2 OCH

2

); 2.67, 2.50 (m, 2H, 2CH); 1.81, 0.96, 0.92 (s, 9H, 3 CH

3 ¹³

C NMR (δ, CDCl

3

): 351.04 (m, Cα); 145.56 (=C); 137.83 (=C(C)H); 122.36-135.13 (Ph, Cβ , =C);

94.10 (Cp); 73.88, 69.59 (2 OCH

2

); 44.99, 39.61 (2 CH); 35.85 (C); 29.72 (CH

2

); 28.12, 24.89, 24.14 (3 CH

3 ³¹

P NMR (δ, CDCl

3

): 40.91 (br, PPh

3

). MS (ESI

⁺

) m/z: 909.2948 (M)

⁺

Synthesis of Compound 11a. The solution of complex 8 (150 mg, 0.16 mmol) in

50

CDCl

3

(1.5 mL) and CH

3

CN (97 mg, 2.4 mmol, 0.12 mL) in an NMR tube was heated at 50

^o

C for 24 h. Then CDCl

3

and CH

3

CN were removed in vacuo and CH

2

(1 mL) was used to extract the product and diethyl ether (6 mL) was then added. The pale-orange precipitates thus formed was filtered and washed with diethyl ether and dried under vacuum to give [Ru]NCCH

3 +

. The filtrate was evaporated to dryness under vacuum and the crude product purified by flash chromatography (silica gel, hexanes/EtOAc = 10/1) to afford 11a (26 mg, 93%). Spectroscopic data of 11a:

The ratio of anti- and syn- isomers is 1:0.5.

Spectroscopic data for the anti-isomer:

¹

H NMR (δ, CDCl

3

): 4.93, 4.84 (s, 2H, =CH

2

);

3.86 (m, 1H, OCH

2

); 3.53, 3.07 (2d, 2H,

² J HH

=11.42 Hz, OCH

2

); 3.12 (t, 1H,

2 J HH

=11.35 Hz, OCH

2

); 2.47 (td, 1H,

² J HH

=11.35 Hz,

³ J HH

=4.49 Hz, CH); 2.28 (dd, 1H,

2 J HH

=11.35 Hz,

⁴ J HH

=2.39 Hz, CH); 2.08 (d, 1H,

⁴ J HH

=2.39 Hz, ≡CH); 1.75, 1.13, 0.97

(s, 9H, 3 CH

3 ¹³

C NMR (δ, CDCl

3

): 143.42 (=C); 113.19 (=CH

2

); 83.26 (≡C); 78.02, 72.15 (2 OCH

2

); 71.14 (≡CH); 45.22, 42.48 (2CH); 33.71 (C); 25.17, 21.13, 19.75 (3 CH

3

). MS (ESI

⁺

) m/z: 179.1422 (M+1)

⁺

Spectroscopic data for the syn-isomer:

¹

H NMR (δ, CDCl

3

): 4.86, 4.54 (s, 2H, =CH

2

);

3.86 (m, 1H, OCH

2

); 3.64 (t, 1H,

² J HH

=10.95 Hz, OCH

2

); 3.48, 3.25 (2d, 2H,

2 J HH

=11.51 Hz, OCH

2

); 2.60 (br, 2H, 2CH); 2.13 (d, 1H,

⁴ J HH

=2.39 Hz, ≡CH); 1.74,

1.16, 1.01 (s, 9H, 3 CH

3 ¹³

C NMR (δ, CDCl

3

): 143.63 (=C); 110.63 (=CH

2

); 81.93 (≡

51

C); 73.32, 73.25 (2 OCH

2

); 66.83 (≡CH); 40.79, 40.20 (2CH); 33.40 (C); 24.80, 22.00, 21.13 (3 CH

3

). MS (ESI

⁺

) m/z: 179.1422 (M+1)

⁺

Synthesis of Compound 11b. The solution of compound 2b (55 mg, 0.24 mmol) and

[Ru]NCCH

3 +

(55 mg, 0.07 mmol) in cosolvent of CHCl

3

/MeOH in an NMR tube was heated at 60

^o

C for 24 h. Then CHCl

3

and MeOH were removed in vacuo and CH

2

(1.0 mL) was used to extract the product and diethyl ether (6.0 mL) was then added.

The filtrate was evaporated to dryness under vacuum and the crude product purified by flash chromatography (silica gel, hexanes/EtOAc = 10/1) to afford 11b (22 mg, 45%).

Spectroscopic data of 11b:

The ratio of anti- and syn- isomers is 1:0.18.

Spectroscopic data for the anti-isomer:

¹

H NMR (δ, CDCl

3

): 5.52 (s, 1H, HC=); 3.84 (dd, 1H,

² J HH

=11.54 Hz,

³ J HH

=4.59 Hz, OCH

2

); 3.08 (t, 1H,

² J HH

=11.54 Hz, OCH

2

);

3.50, 3.04 (2d, 2H,

² J HH

=11.28 Hz, OCH

2

); 2.62 (td, 1H,

³ J HH

=11.50 Hz,

³ J HH

=4.59 Hz, CH); 2.29 (br, 4H, 2 CH

2

); 2.24 (dd, 1H,

³ J HH

=11.50 Hz,

⁴ J HH

=2.11 Hz, CH); 2.04 (d, 1H,

⁴ J HH

=2.11 Hz, HC≡); 1.82 (quintet, 2H,

³ J HH

=7.37 Hz, CH

2

); 1.11, 0.93 (s, 6H,

52

2CH

3 ¹³

C NMR (δ, CDCl

3

): 142.05 (C=); 126.84 (HC=); 83.68 (C≡); 78.01, 72.00 (2 OCH

2

); 71.03 (HC≡); 42.97, 39.85 (2 CH); 33.65 (C); 33.14, 32.26, 23.15 (3 CH

2

);

25.09, 19.74 (2 CH

3

). MS (ESI

⁺

) m/z: 227.1406 (M+Na)

⁺

Spectroscopic data for the syn-isomer:

¹

H NMR (δ, CDCl

3

): 2.06 (d, 1H,

⁴ J HH

=2.41 Hz, HC≡). MS (ESI

⁺

) m/z: 227.1406 (M+Na)

⁺

Synthesis of compound 12 and complex 13 and. A mixture of [Ru]Cl (230 mg, 0.32

mmol), 2a (62 mg, 0.32 mmol), and KPF

6

(77 mg, 0.42 mmol), in MeOH (30 mL) was stirred at 50

^o

C for one day. After that, the solvent of the solution was removed under reduced pressure and then 20mL of CH

2

was added. The solution was filtered through a bed of Celite to remove the insoluble salts, and the pad was eluted with CH

2

until the eluent was colorless, then the solvent of the filtrate were removed under vacuum and the solid residue was extracted with a small volume of CH

2

followed by re-precipitation by a 50 mL of stirred diethyl ether. Precipitates thus formed were collected in a glass frit and dried under vacuum. The final product was obtained as a deep red powder identified as 13 (167 mg, 60% yields). The filtrate was evaporated to dryness under vacuum and the crude product purified by chromatography (silica gel,

53

hexanes/EtOAc = 10/1) to afford 12 ( 20 mg, 30% yields).

Spectroscopic data of 13:

The ratio of anti- and syn-isomers is 1:0.3.

Spectroscopic data for the anti-isomer:

¹

H NMR (δ, CDCl

3

): 6.89-7.49 (m, 40H, Ph);

6.73 (s, 1H, HC(C)=); 4.86 (s, 5H, Cp); 4.41, 2.27 (2d, 2H,

² J HH

=16.49 Hz, CH

2

); 4.01 (dd, 1H,

² J HH

=10.91 Hz,

³ J HH

=4.42 Hz, OCH

2

); 2.72 (t, 1H,

² J HH

=10.91 Hz,OCH

2

);

3.43, 2.97 (2d, 2H,

² J HH

=11.28 Hz, OCH

2

); 1.71 (br, 1H, CH); 1.34 (t, 1H,

³ J HH

= 11.12

Hz, CH

2

); 0.99, 0.91, 0.81 (s, 9H, 3 CH

3 ¹³

C NMR (δ, CDCl

3

): 317.61 (t,

² J CP

=9.66 Hz, Cα); 151.48 (HC=); 148.19 (C=); 128.20-135.84 (Ph); 94.54 (Cp); 79.30 (OCH

2

); 69.04

(OCH

2

); 59.66 (CH

2

); 48.44 (CH); 41.11 (CH); 32.92 (C); 23.32, 20.62, 18.90 (3 CH

3

31

P NMR (δ, CDCl

3

): 45.26, 45.02 (2d,

² J PP

=29.05 Hz, PPh

3

). MS (ESI

⁺

) m/z: 869.2615

(M)

⁺

Spectroscopic data for the syn-isomer:

¹

H NMR (δ, CDCl

3

): 6.89-7.49 (m, 40H, Ph, HC(C)=); 4.86 (s, 5H, Cp); 4.17, 2.80 (2d, 2H,

² J PP

=18.58 Hz,

³ J PP

=3.26 Hz, CH

2

); 3.61 (2d, 1H,

² J HH

=11.06 Hz,

³ J HH

=4.81 Hz, OCH

2

); 3.03 (t, 1H,

² J HH

=11.18 Hz, OCH

2

);

3.43, 3.24 (2d, 2H,

² J HH

=12.51 Hz, OCH

2

); 2.34 (m, 1H, CH); 1.71 (br, 1H, CH); 1.07, 0.95, 0.87 (s, 9H, 3 CH

3 ¹³

C NMR (δ, CDCl

3

): 316.67 (t,

² J CP

=9.66 Hz, Cα); 151.48 (HC=); 148.36 (C=); 128.20-135.84 (Ph); 94.78 (Cp); 72.44 (OCH

2

); 63.19 (OCH

2

);

54.57 (CH

2

); 42.04 (CH); 39.54 (CH); 31.33 (C); 26.16, 23.56, 23.05 (3 CH

3 ³¹

P NMR

54

(δ, CDCl

3

): 46.63, 44.56 (2d,

² J PP

=29.05 Hz, 2 PPh

3

). MS (ESI

⁺

) m/z: 869.2615 (M)

⁺

Spectroscopic data for the major diastereomer 12:

¹

H NMR (δ, CDCl

3

): 5.62 (m, 2H, 2 HC=); 3.86 (dd, 1H,

² J HH

=11.39 Hz,

³ J HH

=4.64Hz, OCH

2

); 3.20 (s, 3H, OCH

3

);

3.15-3.04 (m, 3H, 2 OCH

2

); 2.32 (m, 1H, CH); 1.97 (m, 2H, CH

2

); 1.93 (m, 1H, CH);

1.12, 1.10, 0.89 (s, 9H, 3 CH

3 ¹³

C NMR (δ, CDCl

3

): 126.55, 124.76 (2 CH=); 74.88 (C); 74.01, 65.33 (2 OCH

2

); 48.10 (OCH

3

); 43.45, 36.76 (2 CH); 34.98 (CH

2

); 33.30 (C); 26.22, 23.95, 21.39 (3 CH

3

). MS (ESI

⁺

) m/z: 223.1507 (M+Na)

⁺

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61 Appendix I

X-Ray Crystallographic Data

在文檔中釕金屬誘發含異原子有機烯炔化合物之環化反應的研究 (頁 41-66)

37

1

3

2

2 J HH

2

2

2

3

13

3

2

2

3

+

+

2

2

1

3

2

2

2

3

13

3

2

2

3

+

+

38

4

1

3

3 J HH

4 J HH

2

3 J HH

2 J HH

2

4 J HH

3 J HH

4 J HH

2

2

13

3

2

2

3

+

+

Synthesis of Complex 3. A mixture of [Ru]Cl (250 mg, 0.34 mmol), 1 (61 mg, 0.34

4

6

2

2

2

2

39

2

2

1

3

3 J HH

2

3 J HH

2

2 J HH

2

2

3

13

3

3 J CP

2

2

3

¹

² J HH

¹³

⁺

⁺

¹³

⁺

⁺

³ J HH

⁴ J HH

³ J HH

² J HH

⁴ J HH

³ J HH

⁴ J HH

¹³

⁺

⁺

¹

³ J HH

³ J HH

² J HH

¹³

³ J CP

³¹

² J PP

⁺

⁺

¹

² J HH

² J HH

¹³

² J CP

³¹

⁺

⁺

¹

² J HH

² J HH

² J HH

³ J HH

³ J HH

¹³

³¹

² J PP