Highly selective cobalt-mediated [6 + 2] cycloaddition of cycloheptatriene and allenes

Article abstract of DOI:10.1021/ol102783x

[6 + 2] Cycloadditions between cycloheptatrienes with allenes have been investigated. Cobalt salts were found to promote this transformation efficiently. Moreover, this reaction was found to be highly selective since only one regioisomer was obtained with an excellent E/Z-selectivity.

Full text of DOI:10.1021/ol102783x

Highly selective cobalt-mediated [6+2] cycloaddition of
cycloheptatriene and allenes
Hervé Clavier,* Karel Le Jeune, Innocenzo de Riggi, Alphonse Tenaglia* and Gérard Buono*
Université Aix-Marseille III, UMR CNRS 6263 - Institut des Sciences Moléculaires de Marseille
Av. Escadrille Normandie Niemen, 13397 Marseille Cedex 20, France.
General considerations: ZnCl2, ZnBr2 and ZnI2 were dried under vacuum at 80 °C, then
stored in a glovebox. All other reagents were used as received. Cobalt salts and phoshpine
ligands were also stored in a glovebox. Dichloroethane (DCE) was distilled on calcium
1
hydride. Flash column chromatography was performed on silica gel 60 (230-400 mesh). H
and 13C Nuclear Magnetic Resonance (NMR) spectra were recorded on a Bruker Avance 300
or 400 Ultrashield NMR spectrometers. High Resolution Mass Spectroscopy (HRMS)
analyses were performed on a QStar Elite (Applied Biosystems SCIEX) spectrometer.
Geometries of the exocyclic C-C double bonds were determined by NOESY experiments;
figure below depicted nuclear Overhauser effects observed.
nOe
nOe
R
Ph
H
H
H
H
H
H
H
H3C
nOe
H
H
nOe
General procedure A: Gem dibromocyclopropanation
According to the method of de Land and Brandsma,1 alcene derivative (20 mmol), bromoform
(2.6 mL, 30 mmol, 1.5 equiv.) and triethylbenzylammonium chloride (50 mg, 0.2 mmol, 0.01
equiv.) were stirred vigorously. A solution of sodium hydroxide (3.2 g, 80 mmol, 4 equiv.) in
water (3 mL) was then added in small portions, in order to keep the mixture temperature
below 50 °C. When all the sodium hydroxide had been added, the reaction mixture was stirred
for an additional 2 h at 60 °C. Reaction was quenched by addition of water (20 mL) and
product was extracted with dichloromethane (3 x 50 mL). The combined organic fractions
were washed with brine (50 mL), dried over MgSO4 and volatiles were removed under
reduced pressure. Products were purified either by distillation or silica gel chromatography.
General procedure B: Allene formation from cyclopropane
- 1 -

According to Baird protocol,2 3 M ethylmagnesium bromide in THF (15 mL, 15.0 mmol, 1.5
equiv.) was added to a stirred solution of dibromocyclopropane (10.0 mmol) in dry THF (20
ml) under nitrogen at room temperature. Stirring was continued for 30 min, when water (2 ml)
was added. The organic layer was washed with 1 M hydrochloric acid and extracted with
petroleum ether (2 x 10 mL). The combined organic layers were dried and evaporated in
vacuo. The product was purified by silica gel chromatography.
General procedure C: Cobalt-mediated cycloaddition
In a glovebox, a Schlenk flask, under nitrogen, was charged with dppe (20 mg, 0.05 mmol,
0.05 equiv.), CoI2 (16 mg, 0.05 mmol, 0.05 equiv.) and 1,2-dichloroethane (2 mL). The
mixture was stirred for 10 min and powdered zinc (10 mg, 0.15 mmol, 0.15 equiv.) was
added. Then, 1,3,5-cycloheptatriene (200 µL, 2 mmol, 2 equiv.), a solution of allene (1 mmol,
1 equiv.) in 1,2-dichloroethane (1 mL) and zinc iodide (31 mg, 0.10 mmol, 0.10 equiv.) were
added successively. The resulting mixture was heated at 60 ºC for 5 h. Of note, reaction
progress can be monitored by TLC. After cooling to room temperature, the reaction was
quenched with petroleum ether (5 mL). The reaction mixture was filtered through celite!and
removal of solvent followed by column chromatography on silica gel gave cycloaddition
product.
(E)-7-Benzylidenebicyclo[4.2.1]nona-2,4-diene 1a3
Ph
H
H
According to the general procedure C, a colorless oil was obtained after column
1
chromatography on silica gel (petroleum ether/Et2O 95:5). H NMR (400 MHz, CDCl3): δ =
7.33-7.24 (m, 4H, HPh), 7.17 (t, J(H,H) = 7.2 Hz, 1H, HPh), 6.23 (s, 1H, CH=C), 6.08-6.03 (m,
2H, CH=CH-CH=CH), 5.70-5.63 (m, 2H, CH=CH-CH=CH), 3.49 (t, J(H,H) = 7.6 Hz, 1H,
CH=C-CH), 2.98 (dd, J(H,H) = 16.0 and 1.6 Hz, 1H, CH=C-CH2), 2.88-2.77 (m, 2H, CH=C-
CH2 and CH2-CH-CH2), 2.29 (dt, J(H,H) = 12.0 and 6.4 Hz, 1H, CH-CH2-CH), 2.01 (dd,
13
J(H,H) = 12.0 and 1.6 Hz, 1H, CH-CH2-CH). C NMR (75 MHz, CDCl3): δ = 155.1 (C),
139.7 (CH), 139.3 (C), 137.9 (CH), 129.0 (CH), 126.7 (CH), 124.8 (CH), 124.6 (CH), 121.7
(CH), 48.7 (CH), 44.8 (CH2), 40.1 (CH), 31.1 (CH2). The E geometry of the product was
established by 1H NMR NOE studies.
- 2 -

(E)-7-(4-Methoxybenzylidene)bicyclo[4.2.1]nona-2,4-diene 1b3
OMe
H
H
According to the general procedure C, a colorless oil was obtained after column
1
chromatography on silica gel (petroleum ether/Et2O 95:5). H NMR (300 MHz, CDCl3): δ =
7.22 (d, J(H,H) = 9.0 Hz, 2H, HAr), 6.87 (d, J(H,H) = 9.0 Hz, 2H, HAr), 6.18 (s, 1H, CH=C),
6.10-6.02 (m, 2H, CH=CH-CH=CH), 5.69-5.65 (m, 2H, CH=CH-CH=CH), 3.82 (s, 3H, CH3),
3.47 (t, J(H,H) = 7.2 Hz, 1H, CH=C-CH), 2.95 (d, J(H,H) = 16.2 Hz, 1H, CH=C-CH2), 2.88-
2.74 (m, 2H, CH=C-CH2 and CH2-CH-CH2), 2.29 (dt, J(H,H) = 11.7 and 6.0 Hz, 1H, CH-
CH2-CH), 2.02 (dd, J(H,H) = 11.7 and 1.8 Hz, 1H, CH-CH2-CH). 13C NMR (75 MHz,
CDCl3): δ = 158.5 (C), 153.0 (C), 139.7 (CH), 138.1 (CH), 132.1 (C), 130.1 (CH), 124.5
(CH), 120.9 (CH), 114.4 (CH), 56.0 (CH3), 48.6 (CH), 44.6 (CH2), 40.3 (CH), 32.1 (CH2).
The E geometry of the product was established by 1H NMR NOE studies.
(E)-7-(4-Methylbenzylidene)bicyclo[4.2.1]nona-2,4-diene 1c
Me
H
H
According to the general procedure C, a colorless oil was obtained after column
1
chromatography on silica gel (petroleum ether/Et2O 95:5). H NMR (400 MHz, CDCl3): δ =
7.17 (d, J(H,H) = 8.4 Hz, 2H, HAr), 7.13 (d, J(H,H) = 8.4 Hz, 2H, HAr), 6.20 (s, 1H, CH=C),
6.08-6.03 (m, 2H, CH=CH-CH=CH), 5.69-5.64 (m, 2H, CH=CH-CH=CH), 3.48 (t, J(H,H) =
6.8 Hz, 1H, CH=C-CH), 2.97 (d, J(H,H) = 16.8 Hz, 1H, CH=C-CH2), 2.87-2.78 (m, 2H,
CH=C-CH2 and CH2-CH-CH2), 2.34 (s, 3H, CH3), 2.29 (dt, J(H,H) = 12.0 and 6.4 Hz, 1H,
13
CH-CH2-CH), 2.01 (dd, J(H,H) = 12.4 and 2.0 Hz, 1H, CH-CH2-CH). C NMR (75 MHz,
CDCl3): δ = 153.8 (C), 139.3 (CH), 137.7 (CH), 136.1 (C), 135.9 (C), 129.4 (CH), 128.6
- 3 -

(CH), 124.3 (CH), 124.2 (CH), 121.1 (CH), 48.3 (CH2), 44.4 (CH), 39.7 (CH2), 31.8 (CH),
21.6 (CH3). The E geometry of the product was established by 1H NMR NOE studies. HRMS
(ESI): m/z: calcd for C17H19: 223.1481 [M++H]; found 223.1485.
(E)-7-(2-Methylbenzylidene)bicyclo[4.2.1]nona-2,4-diene 1d
Me
H
H
According to the general procedure C, a colorless oil was obtained after column
1
chromatography on silica gel (petroleum ether/Et2O 95:5). H NMR (400 MHz, CDCl3): δ =
7.13-7.11 (m, 1H, HAr), 7.07-7.00 (m, 3H, HAr), 6.20 (s, 1H, CH=C), 6.04-5.98 (m, 1H,
CH=CH-CH=CH), 5.95-5.90 (m, 1H, CH=CH-CH=CH), 5.61-5.54 (m, 2H, CH=CH-
CH=CH), 3.41 (t, J(H,H) = 7.6 Hz, 1H, CH=C-CH), 2.74-2.65 (m, 2H, CH=C-CH2 and CH2-
CH-CH2), 2.54 (ddd, J(H,H) = 16.4, 7.6 and 2.4 Hz, 1H, CH=C-CH2), 2.21 (ddd, J(H,H) =
11.6, 6.0 and 0.8 Hz, 1H, CH-CH2-CH), 2.17 (s, 3H, CH3), 1.90 (dd, J(H,H) = 12.0 and 2.0
13
Hz, 1H, CH-CH2-CH). C NMR (75 MHz, CDCl3): δ = 154.6 (C), 139.3 (CH), 138.0 (CH),
137.9 (C), 136.4 (C), 130.3 (CH), 128.6 (CH), 126.7 (CH), 125.9 (CH), 124.3 (CH), 124.2
(CH), 119.8 (CH), 47.3 (CH2), 43.8 (CH), 39.4 (CH2), 32.2 (CH), 20.4 (CH3). The E geometry
of the product was established by 1H NMR NOE studies. HRMS (ESI): m/z: calcd for C17H19:
223.1481 [M++H]; found 223.1487.
(E)-7-(2-Phenylethylidene)bicyclo[4.2.1]nona-2,4-diene 1e
Ph
H
H
According to the general procedure C, a colorless oil was obtained after column
1
chromatography on silica gel (petroleum ether/Et2O 95:5). H NMR (400 MHz, CDCl3): δ =
7.32 (t, J(H,H) = 7.6 Hz, 2H, HPh), 7.24-7.20 (m, 3H, HPh), 6.10-6.02 (m, 2H, CH=CH-
CH=CH), 5.74-5.65 (m, 2H, CH=CH-CH=CH), 5.39 (t, J(H,H) = 7.2 Hz, 1H, CH=C), 3.39 (t,
J(H,H) = 7.6 Hz, 1H, CH=C-CH), 3.34 (d, J(H,H) = 7.6 Hz, 2H, CH2-CH=C), 2.84-2.75 (m,
2H, CH=C-CH2 and CH2-CH-CH2), 2.64-2.57 (m, 1H, CH=C-CH2), 2.31 (dt, J(H,H) = 12.0
- 4 -

13
and 6.0 Hz, 1H, CH-CH2-CH), 2.02 (dd, J(H,H) = 12.0 and 2.0 Hz, 1H, CH-CH2-CH). C
NMR (75 MHz, CDCl3): δ = 152.9 (C), 141.8 (C), 139.1 (CH), 138.3 (CH), 128.80 (CH),
128.77 (CH), 126.2 (CH), 124.1 (CH), 123.9 (CH), 119.8 (CH), 45.9 (CH), 42.9 (CH2), 39.1
1
(CH), 36.1 (CH2), 32.7 (CH2). The E geometry of the product was established by H NMR
NOE studies. HRMS (ESI): m/z: calcd for C17H19: 223.1481 [M++H]; found 223.1480.
(E)-3-Bicyclo[4.2.1]nona-2,4-dien-7-ylidene)propan-1-ol 1g
OH
H
H
According to the general procedure C, a colorless oil was obtained after column
1
chromatography on silica gel (dichloromethane). H NMR (300 MHz, CDCl3): δ = 6.02 (t,
J(H,H) = 10.5 Hz, 2H, CH=CH-CH=CH), 5.67-5.57 (m, 2H, CH=CH-CH=CH), 5.15 (t,
J(H,H) = 7.2 Hz, 1H, CH=C), 3.60 (dt, J(H,H) = 6.3 and 2.4 Hz, 2H, CH2-OH), 3.30 (t,
J(H,H) = 7.5 Hz, 1H, CH=C-CH), 2.78-2.65 (m, 2H, CH=C-CH2 and CH2-CH-CH2), 2.41
(ddd, J(H,H) = 16.5, 7.8 and 1.2 Hz, 1H, CH-CH2-CH), 2.28-2.17 (m, 3H, CH=C-CH2 and
13
CH2-CH=C), 1.95 (dd, J(H,H) = 12.0 and 1.8 Hz, 1H, CH-CH2-CH). C NMR (75 MHz,
CDCl3): δ = 155.3 (C), 139.1 (CH), 138.5 (CH), 123.9 (CH), 123.8 (CH), 116.9 (CH), 62.5
(CH2), 45.7 (CH), 43.0 (CH2), 39.1 (CH), 33.4 (CH2), 32.5 (CH2). The E geometry of the
1
product was established by H NMR NOE studies. HRMS (ESI): m/z: calcd for C12H17O:
177.1274 [M++H]; found 177.1274.
(E)-2-Bicyclo[4.2.1]nona-2,4-dien-7-ylidene)ethoxy)tetrahydro-2H-pyran 1h3
OTHP
H
H
According to the general procedure C, a colorless oil was obtained after column
chromatography on silica gel (petroleum ether/Et2O 9:1). Mixture of two diastereomers with
1
ratio 1:1. H NMR (300 MHz, CDCl3): δ = 6.02-5.98 (m, 2H, CH=CH-CH=CH), 5.63-5.69
(m, 2H, CH=CH-CH=CH), 5.32 (t, J(H,H) = 6.3 Hz, 1H, CH=CH2), 5.58 (t, J(H,H) = 3.5 Hz,
1H, CH-O), 4.18-4.11 (m, 1H, CH2-O), 3.99-3.91 (m, 1H, CH2-O), 3.89-3.82 (m, 1H, CH2-O),
3.52-3.44 (m, 1H, CH2-O), 3.33 (t, J(H,H) = 7.8 Hz, 1H, CH=C-CH), 2.78-2.69 (m, 1H,
- 5 -

CH=C-CH2), 2.63 (dd, J(H,H) = 15.6 and 1.8 Hz, 1H, CH2-CH-CH2), 2.57-2.46 (m, 1H,
CH=C-CH2), 2.22-2.18 (m, 1H, CH-CH2-CH), 1.93 (dd, J(H,H) = 12.0 and 1.8 Hz, 1H, CH-
CH2-CH), 1.88-1.78 (m, 2H, CH2THP), 1.75-1.62 (m, 1H, CH2THP), 1.60-1.48 (m, 4H, CH2THP).
13C NMR (75 MHz, CDCl3): δ = 156.0 (C), 155.9 (C), 139.1 (CH), 139.0 (CH), 137.8 (CH),
137.5 (CH), 124.1 (CH), 124.0 (CH), 117.3 (CH), 117.2 (CH), 98.2 (CH), 98.0 (CH), 65.2
(CH2), 62.9 (CH2), 62.6 (CH2), 46.2 (CH), 45.8 (CH), 42.8 (CH2), 42.4 (CH2), 39.1 (CH), 38.9
(CH), 32.3 (CH2), 32.2 (CH2), 31.2 (CH2), 31.1 (CH2), 26.0 (CH2), 20.2 (CH2), 20.2 (CH2).
The E geometry of the product was established by 1H NMR NOE studies.
(E)-2-Bicyclo[4.2.1]nona-2,4-dien-7-ylidene)ethoxy)(tert-butyl)dimethylsilane 1i3
OTBS
H
H
According to the general procedure C, a colorless oil was obtained after column
1
chromatography on silica gel (petroleum ether/Et2O 98:2). H NMR (400 MHz, CDCl3): δ =
5.92 (q, J(H,H) = 9.2 Hz, 2H, CH=CH-CH=CH), 5.58-5.53 (m, 2H, CH=CH-CH=CH), 5.23
(t, J(H,H) = 6.4 Hz, 1H, CH=C), 4.06 (d, J(H,H) = 6.0 Hz, 2H, CH2-OTBS), 3.26 (t, J(H,H) =
7.6 Hz, 1H, CH=C-CH), 2.69 (q, J(H,H) = 7.6 Hz, 1H, CH2-CH-CH2), 2.53 (d, J(H,H) = 16.8
Hz, 1H, CH=C-CH2), 2.47-2.40 (m, 1H, CH-CH2-CH), 2.15 (d, J(H,H) = 12.0 and 5.2 Hz, 1H,
CH=C-CH2), 1.88 (dd, J(H,H) = 12.0 and 1.6 Hz, CH-CH2-CH), 0.84 (s, 9H, C(CH3)3), 0.00
(s, 6H, Si(CH3)2),. 13C NMR (75 MHz, CDCl3): δ = 152.7 (C), 138.9 (CH), 137.7 (CH), 124.0
(CH), 120.8 (CH), 61.9 (CH2), 46.0 (CH), 42.5 (CH2), 39.0 (CH), 32.1 (CH2), 26.4 (CH3),
18.8 (C), -4.6 (CH3), -4.7 (CH3). The E geometry of the product was established by 1H NMR
NOE studies.
(E)-3-Bicyclo[4.2.1]nona-2,4-dien-7-ylidene)propyl benzoate 1j
O
O
Ph
H
H
According to the general procedure C, a colorless oil was obtained after column
1
chromatography on silica gel (petroleum ether/Et2O 95:5). H NMR (300 MHz, CDCl3): δ =
- 6 -

8.08-8.03 (m, 2H, HPh), 7.59-7.55 (m, 1H, HPh), 7.48-7.43 (m, 2H, HPh), 6.03-5.96 (m, 2H,
CH=CH-CH=CH), 5.63-5.57 (m, 2H, CH=CH-CH=CH), 5.22 (t, J(H,H) = 7.2 Hz, 1H,
CH=C), 4.36 (m, 2H, CH2-O), 3.32 (t, J(H,H) = 7.6 Hz, 1H, CH=C-CH), 2.76 (q, J(H,H) =
6.8 Hz, 1H, CH2-CH-CH2), 2.67 (d, J(H,H) = 16.8 Hz, 1H, CH=C-CH2), 2.56-2.49 (m, 1H,
CH=C-CH2), 2.42 (q, J(H,H) = 7.2 Hz, 2H, CH2-CH=C), 2.23 (dt, J(H,H) = 12.0 and 1.8 Hz,
13
1H, CH-CH2-CH), 1.96 (dd, J(H,H) = 12.4 and 1.6 Hz, 1H, CH-CH2-CH). C NMR (75
MHz, CDCl3): δ = 167.0 (C), 154.8 (C), 139.0 (CH), 138.0 (CH), 133.2 (CH), 130.9 (C),
130.0 (CH), 128.7 (CH), 124.0 (CH), 123.8 (CH), 115.9 (CH), 64.6 (CH2), 46.0 (CH), 42.7
(CH2), 38.9 (CH), 32.5 (CH2), 29.6 (CH2). The E geometry of the product was established by
1H NMR NOE studies. HRMS (ESI): m/z: calcd for C19H24NO2: 298.1802 [M++NH4]; found
298.1807.
(E)-2-Bicyclo[4.2.1]nona-2,4-dien-7-ylidene)ethyl)isoindoline-1,3-dione 1k
O
N
O
H
H
According to the general procedure C, a colorless oil was obtained after column
1
chromatography on silica gel (petroleum ether/Et2O 95:5). H NMR (400 MHz, CDCl3): δ =
7.79 (dd, J(H,H) = 5.4 and 3.0 Hz, 2H, HAr), 7.66 (dd, J(H,H) = 5.4 and 3.0 Hz, 2H, HAr), 6.00
(dd, J(H,H) = 11.6 and 7.2 Hz, 1H, CH=CH-CH=CH), 5.88 (t, J(H,H) = 9.2 Hz, 1H, CH=CH-
CH=CH), 5.61-5.54 (m, 2H, CH=CH-CH=CH), 5.24 (t, J(H,H) = 7.6 Hz, 1H, CH=C), 4.15
(d, J(H,H) = 7.2 Hz, 2H, CH2-N), 3.23 (t, J(H,H) = 7.2 Hz, 1H, CH=C-CH), 2.84-2.67 (m,
3H, CH=C-CH2 and CH2-CH-CH2), 2.18 (dt, J(H,H) = 12.0 and 6.2 Hz, 1H, CH-CH2-CH),
1.99 (dd, J(H,H) = 12.0 and 2.0 Hz, 1H, CH-CH2-CH). 13C NMR (75 MHz, CDCl3): δ = 168.4
(C), 156.6 (C), 139.0 (CH), 137.2 (CH), 134.2 (CH), 132.7 (C), 124.2 (CH), 123.9 (CH),
123.5 (CH), 114.4 (CH), 46.0 (CH), 42.6 (CH2), 38.8 (CH), 37.4 (CH2), 32.2 (CH2). The E
1
geometry of the product was established by H NMR NOE studies. HRMS (ESI): m/z: calcd
for C19H18NO2: 292.1332 [M++H]; found 292.1331.
1-(2,2-Dibromocyclopropyl)benzene4
- 7 -

Br
Br
According the general procedure A, a distillation under reduced pressure afforded the product
as orange liquid (4.0 g, 72 %). 1H NMR (200 MHz, CDCl3): δ = 7.49-7.31 (m, 5H, HPh), 3.03
(dd, J(H,H) = 10.2 and 8.6 Hz, 1H, CH), 2.21 (dd, J(H,H) = 10.2 and 7.6 Hz, 1H, CH2), 2.08
13
(dd, J(H,H) = 8.6 and 7.6 Hz, 1H, CH2). C NMR (75 MHz, CDCl3): δ = 138.8 (C), 129.7
(CH), 129.3 (CH), 127.7 (CH), 35.8 (C), 28.7 (CH), 26.7 (CH2).
Propa-1,2-dien-1-ylbenzene 4a2
•
Ph
According to the general procedure B a colorless oil was obtained (1 g, 86 % yield). 1H NMR
(200 MHz, CDCl3): δ = 7.32-7.17 (m, 5H, HPh), 6.17 (t, J(H,H) = 6.7 Hz, 1H, CH), 5.15 (d,
13
J(H,H) = 6.7 Hz, 2H, CH2). C NMR (75 MHz, CDCl3): δ = 209.7 (C), 133.8 (C), 128.5
(CH), 126.8 (CH), 126.6 (CH), 93.9 (CH), 78.6 (CH2).
1-(2,2-Dibromocyclopropyl)-4-methoxybenzene5
Br
Br
MeO
According the general procedure A, a silica gel chromatography (eluent: petroleum ether)
afforded the product as orange liquid (5.5 g, 90 %). 1H NMR (300 MHz, CDCl3): δ = 7.20 (d,
J(H,H) = 8.7 Hz, 2H, HAr), 6.91 (d, J(H,H) = 8.7 Hz, 2H, HAr), 3.84 (s, 3H, CH3), 2.92 (dd,
J(H,H) = 10.5 and 8.1 Hz, 1H, CH2), 2.12 (dd, J(H,H) = 10.5 and 7.5 Hz, 1H, CH2), 1.97 (t,
J(H,H) = 8.1 Hz, 1H, CH). 13C NMR (75 MHz, CDCl3): δ = 159.4 (C), 130.4 (CH), 128.6 (C),
114.1 (CH), 55.7 (CH3), 35.7 (CH), 29.7 (C), 27.7 (CH2).
1-Methoxy-4-(propa-1,2-dien-1-yl)benzene 4b6
•
MeO
1
According to the general procedure B a colorless oil was obtained (1.4 g, 96 % yield). H
NMR (300 MHz, CDCl3): δ = 7.26 (d, J(H,H) = 8.7 Hz, 2H, HAr), 6.90 (d, J(H,H) = 8.7 Hz,
2H, Har), 6.17 (t, J(H,H) = 6.6 Hz, 1H, CH), 5.16 (d, J(H,H) = 6.6 Hz, 2H, CH2), 3.83 (s, 3H,
- 8 -

13
CH3). C NMR (75 MHz, CDCl3): δ = 209.8 (C), 159.2 (C), 128.2 (CH), 126.6 (C), 114.6
(CH), 93.8 (CH), 79.1 (CH2), 55.7 (CH3).
1-(2,2-Dibromocyclopropyl)-4-methylbenzene7
Br
Br
Me
According the general procedure A, a silica gel chromatography (eluent: petroleum ether)
1
afforded the product as orange liquid (5.6 g, 97 %). H NMR (300 MHz, CDCl3): δ = 7.21-
7.15 (m, 4H, HAr), 2.94 (dd, J(H,H) = 10.5 and 8.1 Hz, 1H, CH), 2.38 (s, 3H, CH3), 2.13 (dd,
J(H,H) = 10.5 and 7.5 Hz, 1H, CH2), 2.00 (dd, J(H,H) = 8.1 and 7.5 Hz, 1H, CH2). 13C NMR
(75 MHz, CDCl3): δ = 138.2 (C), 133.8 (C), 129.8 (CH), 129.5 (CH), 36.5 (C), 29.7 (CH),
28.0 (CH2), 22.0 (CH3).
1-Methyl-4-(propa-1,2-dien-1-yl)benzene 4c8
•
Me
1
According to the general procedure B a colorless oil was obtained (0.52 g, 80 % yield). H
NMR (300 MHz, CDCl3): δ = 7.21 (d, J(H,H) = 8.4 Hz, 2H, HAr), 7.14 (d, J(H,H) = 8.4 Hz,
2H, HAr), 6.16 (t, J(H,H) = 6.6 Hz, 1H, CH), 5.16 (d, J(H,H) = 6.6 Hz, 2H, CH2), 2.35 (s, 3H,
13
CH3). C NMR (75 MHz, CDCl3): δ = 210.4 (C), 137.4 (C), 131.7 (C), 130.1 (CH), 127.4
(CH), 94.5 (CH), 79.5 (CH2), 22.0 (CH3).
1-(2,2-Dibromocyclopropyl)-2-methylbenzene9
Me
Br
Br
According the general procedure A, a silica gel chromatography (eluent: petroleum ether)
1
afforded the product an orange liquid (2.4 g, 41 %). H NMR (300 MHz, CDCl3): δ = 7.14-
7.09 (m, 2H, HAr), 7.06-7.00 (m, 1H, HAr), 6.84 (d, J(H,H) = 7.8 Hz, 1H, HAr), 2.69 (br t,
J(H,H) = 8.7 Hz, 1H, CH), 2.37 (s, 3H, CH3), 2.01 (dd, J(H,H) = 10.2 and 7.5 Hz, 1H, CH2),
13
1.91 (t, J(H,H) = 8.7 Hz, 1H, CH2). C NMR (75 MHz, CDCl3): δ = 210.8 139.4 (C), 135.7
(C), 130.2 (CH), 128.0 (CH), 127.9 (CH), 126.1 (CH), 35.6 (CH), 28.7 (C), 27.1 (CH2), 20.5
(CH3).
- 9 -

1-Methyl-2-(propa-1,2-dien-1-yl)benzene 4d10
•
1
According to the general procedure B a colorless oil was obtained (1.25 g, 96 % yield). H
NMR (300 MHz, CDCl3): δ = 7.42 (d, J(H,H) = 7.5 Hz, 1H, HAr), 7.22-7.14 (m, 3H, HAr),
6.38 (t, J(H,H) = 6.9 Hz, 1H, CH), 5.14 (d, J(H,H) = 6.9 Hz, 2H, CH2), 2.39 (s, 3H, CH3). 13C
NMR (75 MHz, CDCl3): δ = 210.4 (C), 135.3 (C), 132.5 (C), 130.8 (CH), 127.6 (CH), 127.2
(CH), 126.5 (CH), 91.6 (CH), 78.4 (CH2), 20.2 (CH3).
((2,2-Dibromocyclopropyl)methyl)benzene11
Br
Br
According the general procedure A, a silica gel chromatography (eluent: petroleum ether)
1
afforded the product as yellow liquid (2.2 g, 38 %). H NMR (300 MHz, CDCl3): δ = 7.44-
7.25 (m, 5H, HAr), 3.11 (dd, J(H,H) = 15.6 and 6.3 Hz, 1H, CH), 2.83 (dd, J(H,H) = 15.6 and
13
6.3 Hz, 1H, CH), 1.97-1.88 (m, 2H, CH2), 1.47 (t, J(H,H) = 6.3 Hz, 1H, CH). C NMR (75
MHz, CDCl3): δ = 139.9 (C), 129.3 (CH), 129.0 (CH), 127.2 (CH), 38.9 (CH2), 32.6 (CH),
29.7 (C), 29.2 (CH2).
Buta-2,3-dien-1-ylbenzene 4e11
Ph
•
1
According to the general procedure B a colorless oil was obtained (0.80 g, 85 % yield). H
NMR (300 MHz, CDCl3): δ = 7.42-7.21 (m, 5H, HAr), 5.33 (quint, J(H,H) = 7.2 Hz, 1H, CH),
4.76 (dt, J(H,H) = 2.7 and 7.2 Hz, 2H, CH2=C), 3.41 (dt, J(H,H) = 2.7 and 7.2 Hz, 2H, CH2-
13
CH). C NMR (75 MHz, CDCl3): δ = 209.4 (C), 140.7 (C), 128.9 (CH), 128.8 (CH), 126.6
(CH), 90.0 (CH), 75.5 (CH2), 35.5 (CH2).
Buta-2,3-dien-1-ol 4f12
HO
•
- 10 -

A solution of 4-chlorobut-2-yn-1-ol (2.08 mg, 20 mmol) in Et2O (20 mL) was added to a
suspension of LiAlH4 (836 mg, 22 mmol, .1 equiv.) in Et2O (40 mL) at 0 ̊C. The resultant
reaction mixture was warmed up to room temperature and stirred for 1 h before adding water.
The aqueous layer was extracted with Et2O. The combined organic layers were washed with
brine, dried over MgSO4, filtered and concentrated under vacuum. Flash chromatography on
silica gel (petroleum ether/Et2O 7:3) afforded but-3,4-dien-1-ol as colorless oil (1.1 g, 79 %).
1H NMR (300 MHz, CDCl3): δ = 5.32 (quint, J(H,H) = 6.6 Hz, 1H, CH), 4.83 (dt, J(H,H) =
3.0 and 6.6 Hz, 2H, CH2=C), 4.13 (dt, J(H,H) = 3.0 and 6.6 Hz, 2H, CH2-CH), 2.38 (s, 1H,
OH). 13C NMR (75 MHz, CDCl3): δ = 208.3 (C), 91.2 (CH), 77.3 (CH2), 60.6 (CH2).
Penta-3,4-dien-1-ol 4g13
•
HO
Diisopropylamine (2.8 mL, 20 mmol, 2 equiv.) was added to a stirred mixture of the but-3-yn-
1-ol (750 µL, 10 mmol), paraformaldehyde (600 mg, 20 mmol, 2 equiv.) and copper bromide
(737 mg, 3.3 mmol, 0.33 equiv.) in dioxane (0.1 M). The reaction was heated to reflux for 6
hours, then cooled to room temperature. Volatiles were removed under reduced pressure and
the resulting crude material chromatographed on silica gel (petroleum ether/Et2O 1:1)
affording the desired product as yellow oil (445 mg, 53 %). 1H NMR (400 MHz, CDCl3): δ =
5.06 (quint, J(H,H) = 6.8 Hz, 1H, CH), 4.66 (dt, J(H,H) = 6.8 and 3.2 Hz, 2H, CH2=C), 3.65
13
(t, J(H,H) = 6.8 Hz, 2H, CH2-CH), 2.24-2.18 (m, 2H, CH2-OH), 1.61 (s, 1H, OH). C NMR
(100 MHz, CDCl3): δ = 209.1 (C), 86.5 (CH), 75.3 (CH2), 62.0 (CH2), 31.6 (CH2).
2-(Buta-2,3-dien-1-yloxy)tetrahydro-2H-pyran 4h14
THPO
•
To a solution of bis-THP protected but-2-yne-1,4-diol (2.54 g, 10.0 mmol) in ether (20 mL)
was added LAH (455 mg, 12.0 mmol, 1.2 equiv.) and the resulting suspension was refluxed
for 4 h. The reaction mixture was quenched with ~2 g of celite/Na2SO4/water (3/3/1) mixture
and was further stirred for 1 h. The insoluble material was filtered and the evaporation of
solvent, followed by flash chromatography (petroleum ether/diethyl ether = 9:1) of the
resulting residue gave a colorless liquid (700 mg, 45 % yield). 1H NMR (300 MHz, CDCl3): δ
= 5.30-5.21 (m, 1H, CH=C), 4.77 (dt, J(H,H) = 6.6 and 2.7 Hz, 2H, CH2=C), 4.68 (t, J(H,H) =
3.5 Hz, 1H, CH-O), 4.26-4.18 (m, 1H, CH2-CH-O), 4.08-4.00 (m, 1H, CH2-CH-O), 3.90-3.83
- 11 -

(m, 1H, CH2-CH2-O), 3.54-3.47 (m, 1H, CH2-CH2-O), 1.88-1.49 (m, 6H, CH2THP). C NMR
13
(75 MHz, CDCl3): δ = 209.7 (C), 98.0 (CH), 88.2 (CH), 76.0 (CH2), 65.2 (CH2), 62.5 (CH2),
30.6 (CH2), 25.8 (CH2), 19.8 (CH2).
(Buta-2,3-dien-1-yloxy)(tert-butyl)dimethylsilane 4i15
TBSO
•
To a stirred solution of buta-2,3-dien-1-ol (420 mg, 6 mmol, 1.2 equiv.) and imidazole (680
mg, 10 mmol, 2 equiv.) in dry DCM (20 mL) was added dropwise at 0 °C, tert-
butyldimethylsilyl chloride (750 mg, 5 mmol, 1 equiv.). The reaction mixture was stirred at
room temperature for 3 days. The reaction was quenched with saturated aqueous ammonium
chloride and extracted with dichloromethane. The combined organics were washed with
brine, dried with magnesium sulfate, filtered, and concentrated under reduced pressure. The
product was purified by silica gel chromatography (petroleum ether/diethyl ether = 99:1) to
1
give a colorless liquid (900 mg, 98 % yield). H NMR (300 MHz, CDCl3): δ = 4.97 (quint,
J(H,H) = 6.4 Hz, 1H, CH), 4.50 (dt, J(H,H) = 2.8 and 6.4 Hz, 2H, CH2=C), 3.94 (dt, J(H,H) =
13
2.8 and 6.4 Hz, 2H, CH2-CH), 0.65 (s, 9H, C(CH3)3), -0.18 (s, 6H, Si(CH3)2). C NMR (75
MHz, CDCl3): δ = 208.4 (C), 91.3 (CH), 76.4 (CH2), 61.8 (CH2), 29.5 (C), 26.3 (CH3), 4.7
(CH3).
Penta-3,4-dien-1-yl benzoate 4j16
•
PhOCO
To a stirred solution of penta-3,4-dien-1-ol (200 mg, 2.5 mmol) and pyridine (400 µL, 5
mmol, 2 equiv.) in dry DCM (10 mL) was added dropwise 0 °C, benzoyl chloride (440 µL,
3.75 mmol, 1.5 equiv.). The reaction mixture was stirred overnight at room temperature. The
reaction was diluted with Et2O and successively washed with HCl 1N (3 x 10 mL) and brine
(50 mL), dried over MgSO4 and the solvent was removed under reduced pressure. The
product was purified by silica gel chromatography (petroleum ether/diethyl ether = 98:2) to
1
give a colorless liquid (456 mg, 97 % yield). H NMR (400 MHz, CDCl3): δ = 8.07 (dd,
J(H,H) = 1.2 and 7.6 Hz, 2H, HPh), 7.58 (tt, J(H,H) = 1.2 and 7.6 Hz, 1H, HPh), 7.46 (t, J(H,H)
= 7.6 Hz, 2H, HPh), 5.20 (quint, J(H,H) = 6.8 Hz, 1H, CH), 4.74 (dt, J(H,H) = 3.2 and 6.8 Hz,
13
2H, CH2=C), 4.42 (t, J(H,H) = 6.8 Hz, 2H, CH2-CH), 2.53-2.47 (m, 2H, CH2-O). C NMR
- 12 -

(75 MHz, CDCl3): δ = 209.6 (C), 169.9 (C), 133.3 (CH), 130.7 (C), 130.0 (CH), 128.7 (CH),
86.3 (CH), 75.9 (CH2), 64.4 (CH2), 28.3 (CH2).
2-(Buta-2,3-dien-1-yl)isoindoline-1,3-dione 4k17
O
N
•
O
To a stirred solution of phtalimide (735 mg, 5 mmol) in THF (20 mL) were added
successively triphenylphosphine (1.57 g, 6 mmol, 1.2 equiv.), buta-2,3-dien-1-ol (420 mg, 6
mmol, 1.2 equiv.), and diisopropylcarbodiimide (DIAD) (1.2 mL, 6 mmol, 1.2 equiv) at 0 °C.
The reaction was warmed to room temperature over 30 min and was stirred at room
temperature for 2 h. The solvent was removed under reduced pressure, and the residue was
purified by column chromatography on silica gel (hexane:Et2O = 9:1) to give a white solid
(960 mg, 96 % yield). 1H NMR (300 MHz, CDCl3): δ = 7.86 (dd, J(H,H) = 3.9 and 9.3 Hz,
2H, HAr), 7.72 (dd, J(H,H) = 3.9 and 9.3 Hz, 2H, HAr), 5.27 (quint, J(H,H) = 6.6 Hz, 1H, CH),
4.81 (dt, J(H,H) = 2.7 and 6.6 Hz, 2H, CH2=C), 4.31 (dt, J(H,H) = 2.7 and 6.6 Hz, 2H, CH2-
13
CH). C NMR (75 MHz, CDCl3): δ = 208.9 (C), 168.2 (C), 134.4 (CH), 132.5 (C), 123.7
(CH), 86.6 (CH), 78.2 (CH2), 36.6 (CH2).
Ethyl buta-2,3-dienoate 4l18
•
CO2Et
To a solution of PPh3 (2.62 g, 10 mmol) in toluene (20 mL), ethyl bromoacetate (1.1 mL, 10
mmol, 1 equiv.) over 15 minutes. The reaction mixture was stirred at room temperature for 2
hours and the precipitate filtered, washed with cold toluene and dried. The collected
phosphonium salt was dissolved in water (50 mL) and 1 drop of phenolphthalein solution was
added. The mixture was cooled in an ice bath and saturated aqueous NaOH was added
dropwise until a permanent pink color was obtained. The solid was filtered and washed with
cold water, collected and dried in vacuo to afford the corresponding ylide which was directly
engaged in the next step. To a solution of stabilized ylide, and triethylamine (1.4 mL, 10
mmol, 1 equiv.) in dry DCM (30 mL) acetyl chloride (0.9 mL, 10 mmol, 1 equiv.) in solution
in DCM (5 mL) was added dropwise. After completion of the reaction (TLC), the solution
was concentrated to afford a gummy residue. This was treated with hexane (25 mL), stirred
- 13 -

vigorously, and allowed for standing for 2 hours. The mixture was filtered and the filtrate
evaporated and passed through a short pad of silica gel to afford the pure product as a
colorless oil (0.85 g, 75 % yield, 2 steps). 1H NMR (300 MHz, CDCl3): δ = 5.63 (t, J(H,H) =
6.6 Hz, 1H, CH2=C), 5.21 (d, J(H,H) = 6.6 Hz, 2H, CH=C), 4.20 (q, J(H,H) = 7.2 Hz, 2H,
13
CH2-CH3), 1.28 (t, J(H,H) = 7.2 Hz, 3H, CH3). C NMR (75 MHz, CDCl3): δ = 216.7 (C),
205.0 (C), 95.7 (CH), 79.5 (CH2), 66.2 (CH2), 14.6 (CH3).
Diphenyl(propa-1,2-dien-1-yl)phosphine oxide 4m19
O
•
P
Ph
Ph
To a solution of prop-2-yn-1-ol (600 µL, 10.0 mmol) and triethylamine (2.1 mL,15 mmol, 1.5
equiv.) in dry THF (30 mL) was added chlorodiphenylphosphine (2.7 mL, 15.0 mmol, 1.5
equiv.) dropwise at -78 °C. After the addition, the cooling bath was removed, and the reaction
mixture was allowed for warming up to room temperature. After complete conversion the
mixture was filtered off. Evaporation of the solvent and flash chromatography on silica gel
1
(eluent: petroleum ether/ether) afforded the product as white solid (1.2 g, 50 % yield). H
NMR (300 MHz, CDCl3): δ = 7.79-7.72 (m, 4H, HPh), 7.53-7.46 (m, 6H, HPh), 5.85 (dt,
13
J(H,H) = 6.9 and 3.9 Hz, 1H, CH), 4.88 (dd, J(H,H) = 11.1 and 6.9 Hz, 2H, CH2). C NMR
(CDCl3, 75 MHz): δ = 214.5 (C), 132.8 (d, J(P,C) = 107.2 Hz, C), 132.4 (d, J(P,C) = 2.2 Hz,
CH), 131.8 (d, J(P,C) = 9.8 Hz, CH), 128.8 (d, J(P,C) = 12.3 Hz, CH), 85.0 (d, J(P,C) = 103.6
Hz, CH), 76.9 (d, J(P,C) = 12.5 Hz, CH2). 31P NMR (121 MHz, CDCl3): δ = 24.5.
(2,2-Dibromo-1-methylcyclopropyl)benzene20
Br
Br
Ph
Me
According the general procedure A, a silica gel chromatography (eluent: petroleum ether)
afforded the product as white solid (4.76 g, 82 %). 1H NMR (300 MHz, CDCl3): δ = 7.42-7.28
(m, 5H, HPh), 2.19 (d, J = J(H,H) = 7.5 Hz, 1H, CH2), 1.81 (d, J = J(H,H) = 7.5 Hz, 1H, CH2),
1.75 (s, 3H, CH3). 13C NMR (75 MHz, CDCl3): δ = 142.8 (C), 128.9 (CH), 128.8 (CH), 127.7
(CH), 37.2 (C), 36.2 (C), 34.1 (CH2), 28.2 (CH3).
Buta-2,3-dien-2-ylbenzene 5a21
- 14 -

Me
•
Ph
1
According to the general procedure B a colorless oil was obtained (0.95 g, 73 % yield). H
NMR (300 MHz, CDCl3): δ = 7.44 (d, J(H,H) = 7.2 Hz, 2H, HPh), 7.35 (t, J(H,H) = 7.2 Hz,
2H, HPh), 7.23 (t, J(H,H) = 7.2 Hz, 1H, HPh), 5.05 (q, J(H,H) = 3.2 Hz, 2H, CH2), 2.13 (t,
13
J(H,H) = 3.2 Hz, 3H, CH3). C NMR (75 MHz, CDCl3): δ = 209.4 (C), 137.1 (C), 128.7
(CH), 126.9 (CH), 126.1 (CH), 100.2 (C), 77.3 (CH2), 17.1 (CH3).
(2,2-Dibromocyclopropane-1,1-diyl)dibenzene22
Br
Br
Ph
Ph
According the general procedure A, a silica gel chromatography (eluent: petroleum ether)
afforded the product as white solid (5.0 g, 71 %). 1H NMR (300 MHz, CDCl3): δ = 7.58-7.54
(m, 4H, HPh), 7.39-7.33 (m, 4H, HPh), 7.30-7.24 (m, 2H, HPh), 2.52 (s, 2H, CH2). 13C NMR (75
MHz, CDCl3): δ = 142.3 (C), 129.7 (CH), 128.9 (CH), 127.8 (CH), 45.5 (C), 35.0 (CH2), 34.4
(C).
Propa-1,2-diene-1,1-diyldibenzene 5b3
Ph
•
Ph
According to the general procedure B a yellow oil was obtained (1.8 g, 84 % yield). 1H NMR
(300 MHz, CDCl3): δ = 7.47-7.27 (m, 10H, HPh), 5.31 (s, 2H, CH2). C NMR (75 MHz,
13
CDCl3): δ = 210.3 (C), 136.7 (C), 128.8 (CH), 127.6 (CH), 109.6 (C), 78.4 (CH2).
(E)-7-(1-Phenylethylidene)bicyclo[4.2.1]nona-2,4-diene 6a
Ph
Me
H
H
According to the general procedure C conducted at 90 °C for 16 h, a colorless oil was
1
obtained after column chromatography on silica gel (petroleum ether/Et2O 95:5). H NMR
(400 MHz, CDCl3): δ = 7.24-7.18 (m, 3H, HPh), 7.05 (d, J(H,H) = 8.0 Hz, 2H, HPh), 6.08 (dd,
J(H,H) = 12.0 and 7.6 Hz, 1H, C-CH=CH), 5.82 (dd, J(H,H) = 12.0 and 7.6 Hz, 1H, CH2-
- 15 -

CH=CH), 5.61-5.54 (m, 2H, CH=CH-CH=CH), 3.47 (t, J(H,H) = 7.8 Hz, 1H, C=C-CH), 2.60
(m, 1H, CH=CH-CH2), 2.47-2.35 (m, 1H, C=C-CH2), 2.24-2.18 (m, 1H, CH-CH2-CH), 1.93
13
(s, 3H, CH3), 1.92 (m, 2H, CH-CH2-CH and C=C-CH2). C NMR (75 MHz, CDCl3): δ =
146.9 (C), 144.8 (C), 138.3 (CH), 136.6 (CH), 128.4 (CH), 128.2 (CH), 127.3 (C), 126.3
(CH), 124.3 (CH), 123.9 (CH), 46.5 (CH2), 43.7 (CH), 40.3 (CH), 33.2 (CH2), 23.4 (CH3).
1
The E geometry of the product was established by H NMR NOE studies. Traces (> 5%) of
presumably Z-isomer could also be observed by 1H NMR. HRMS (ESI): m/z: calcd for C17H19:
223.1481 [M++H]; found 223.1481.
(E)-7-Benzylidenebicyclo[4.2.1]non-3-ene-2,5-diyl diacetate 7
Ph
H
H
AcO
OAc
To a solution of palladium acetate (11 mg, 0.05 mmol, 0.05 equiv.), p-benzoquinone (22 mg,
0.2 mmol, 0.2 equiv.), lithium acetate (510 mg, 5 mmol, 5 equiv.) and MnO2 (103 mg, 1.2
mmol, 1.2 equiv) in acetic acid (2 mL), triene 1a (208 mg, 1 mmol) was added in solution in
pentane (2 mL). The reaction mixture was stirred for 48 h at 30 °C, then diluted with brine
(10 mL) and 1M NaOH solution (50 mL) and extracted with Et2O (3 x 100 mL). The organic
phase was dried over magnesium sulfate and volatiles were removed in vacuo. The crude
product was purified by column chromatography on silica gel (pentane/Et2O, 8:2) to give the
desired product (243 mg, 75 % yield) with a diastereomeric ratio of 80/20. After
recrystallization in pentane/Et2O, the major diastereomer was obtained in a pure form as a
1
white solid (183 mg, 56 % yield). Major diastereomer: H NMR (400 MHz, CDCl3): δ =
7.37-7.31 (m, 4H, HPh), 7.24-7.20 (m, 1H, HPh), 6.54 (s, 1H, CH=C), 5.68 (dt, J(H,H) = 5.2
and 1.2 Hz, 2H, CH=CH), 5.44 (t, J(H,H) = 4.8 Hz, 1H, CH-OAc), 5.33 (t, J(H,H) = 4.0 Hz,
1H, CH-OAc), 3.21 (s, 1H, CH=C-CH), 2.89 (ddd, J(H,H) = 18.0, 9.2 and 1.2 Hz, 1H,
CH=C-CH2), 2.81-2.77 (m, 1H, CH2-CH-CH2), 2.52 (d, J(H,H) = 18.0 Hz, 1H, CH=C-CH2),
2.35 (d, J(H,H) = 13.5 Hz, 1H, CH-CH2-CH), 2.15 (s, 3H, CH3), 2.12 (s, 3H, CH3), 1.88 (dt,
13
J(H,H) = 13.6 and 7.6 Hz, 1H, CH-CH2-CH). C NMR (100 MHz, CDCl3): δ = 170.5 (C),
170.3 (C), 143.5 (C), 128.8 (CH), 128.4 (C), 127.9 (CH), 126.5 (CH), 124.5 (CH), 75.2 (CH),
74.8 (CH), 49.0 (CH), 41.3 (CH), 34.6 (CH2), 27.5 (CH2), 21.5 (CH3), 21.4 (CH3). The minor
diastereoisomer was obtained as yellow oil in the liquid mother (42 mg, 13 % yield) Minor
- 16 -

1
diastereomer: H NMR (400 MHz, CDCl3): δ = 7.37-7.31 (m, 4H, HPh), 7.24-7.20 (m, 1H,
HPh), 6.48 (s, 1H, CH=C), 5.62-5.58 (m, 2H, CH=CH), 5.52-5.48 (m, 1H, CH-OAc), 5.39 (t,
J(H,H) = 6.0 Hz, 1H, CH-OAc), 3.23-3.19 (s, 1H, CH=C-CH), 2.93-2.90 (m, 1H, CH=C-
CH2), 2.81-2.77 (m, 1H, CH2-CH-CH2), 2.68-2.62 (m, 1H, CH=C-CH2), 2.13 (s, 3H, CH3),
13
2.11 (s, 3H, CH3), 2.10-2.05 (m, 2H, CH-CH2-CH). C NMR (75 MHz, CDCl3): δ = 170.5
(C), 170.3 (C), 144.7 (C), 137.9 (C), 128.3 (CH), 128.2 (C), 126.4 (CH), 124.9 (CH), 123.7
(CH), 76.4 (CH), 74.3 (CH), 48.8 (CH), 40.6 (CH), 32.0 (CH2), 28.9 (CH2), 21.5 (CH3), 21.4
(CH3). HRMS (ESI): m/z: calcd for C20H22O4Na: 349.1410 [M++Na]; found 349.1414.
- 17 -

Ph
H
H
1a
1H NMR,
CDCl3, 400 MHz
Ph
H
H
1a
13C NMR,
CDCl3, 75 MHz
- 18 -

OMe
H
H
1b
1H NMR,
CDCl3, 300 MHz
OMe
H
H
1b
13C NMR,
CDCl3, 75 MHz
- 19 -

Me
H
H
1c
1H NMR,
CDCl3, 400 MHz
Me
H
H
1c
13C NMR,
CDCl3, 75 MHz
- 20 -

Me
H
H
1d
1H NMR,
CDCl3, 400 MHz
Me
H
H
1d
13C NMR,
CDCl3, 75 MHz
- 21 -

Ph
H
H
1e
1H NMR,
CDCl3, 400 MHz
Ph
H
H
1e
13C NMR,
CDCl3, 75 MHz
- 22 -

OH
H
H
1g
1H NMR,
CDCl3, 300 MHz
OH
H
H
1g
13C NMR,
CDCl3, 75 MHz
- 23 -

OTHP
H
H
1h
1H NMR,
CDCl3, 300 MHz
OTHP
H
H
1h
13C NMR,
CDCl3, 75 MHz
- 24 -

OTBS
H
H
1i
1H NMR,
CDCl3, 400 MHz
OTBS
H
H
1i
13C NMR,
CDCl3, 75 MHz
- 25 -

O
O
Ph
H
H
1j
1H NMR,
CDCl3, 300 MHz
O
O
Ph
H
H
1j
13C NMR,
CDCl3, 75 MHz
- 26 -

O
N
O
H
H
1k
1H NMR,
CDCl3, 400 MHz
O
N
O
H
H
1k
13C NMR,
CDCl3, 75 MHz
- 27 -

Ph
Me
H
H
6a
1H NMR,
CDCl3, 400 MHz
Ph
Me
H
H
6a
13C NMR,
CDCl3, 75 MHz
- 28 -

Ph
H
H
AcO
OAc
7 (dr = 80:20)
1H NMR,
CDCl3, 400 MHz
Ph
H
H
AcO
OAc
7 (dr = 80:20)
13C NMR,
CDCl3, 75 MHz
- 29 -

Ph
H
H
AcO
OAc
7 exo
1H NMR,
CDCl3, 400 MHz
Ph
H
H
AcO
OAc
7 exo
13C NMR,
CDCl3, 75 MHz
- 30 -