Tertiary alcohols by tandem β-carbolithiation and N→C aryl migration in enol carbamates

Article abstract of DOI:10.1021/ol2029355

Enol carbamates (O-vinylcarbamates) derived from aromatic or α,β-unsaturated compounds and bearing an N-aryl substituent undergo carbolithiation by nucleophilic attack at the (nominally nucleophilic) β position of the enol double bond. The resulting carbamate-stabilized allylic, propargylic, or benzylic organolithium rearranges with N→C migration of the N-aryl substituent, creating a quaternary carbon α to O. The products may be readily hydrolyzed to yield multiply branched tertiary alcohols in a one-pot tandem reaction, effectively a polarity-reversed nucleophilic β-alkylation-electrophilic α-arylation of an enol equivalent.

Full text of DOI:10.1021/ol2029355

Tertiary alcohols by tandem β-carbolithiation and N→C aryl migration in
enol carbamates
Anne M. Fournier; Jonathan Clayden*
School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK
E-mail: clayden@man.ac.uk
SUPPORTING INFORMATION
Table of Contents
1
2
2
2
4
5
. General information ................................................................................................. S1-S2
. Experimental procedures.......................................................................................... S2-S5
.1 Preparation of the starting materials ...................................................................... S5-S18
.2 Carbolithiation and N→C Aryl Migration ............................................................. S18-S37
References for Supporting Information..................................................................... S37
1
13
H/ C NMR spectra.................................................................................................. S38-S95
1
. General information
1
Proton nuclear magnetic resonance ( H NMR) spectra and carbon nuclear magnetic
1
3
resonance ( C NMR) were recorded on a Bruker Ultrashield 400 (400 MHz) spectrometer
with residual non-deuterated solvent as the internal standard. NMR data are presented as
follows: chemical shift δ (in parts per million (ppm) downfield of trimethylsilane),
multiplicity, integration, coupling constant J (in Hz) and assignment (based on chemical shift,
integration, coupling pattern and COSY, DEPT and HMQC NMR experiments when
necessary). Splitting patterns are abbreviated as follows: singlet (s), doublet (d), triplet (t),
quartet (q), quintet (qn), septet (sept), multiplet (m), broad (br), or a combination of these. The
solvent used was deuterated chloroform (δ H: CDCl 7.26 ppm; δ C: CDCl 77.0 ppm).
3
3
Low and high resolution mass spectra were recorded by staff at the University of
Manchester. ES spectra were recorded on a Micromass Platform II; High resolution mass
1

spectra (accurate mass measurement) were recorded on a Thermo Finnigan MAT 95XP mass
spectrometer, and are accurate to ± 0.001 Da.
Infrared spectra were recorded on an ATi Perkin Elmer Spectrum RX1 FTIR
spectrometer and only absorption maxima (υmax) of interest are reported and quoted as
–
1
wavenumbers (cm ). All samples were run as evaporated films on a sodium chloride plate.
Melting points (M.P.) were determined on a Kofler microscope melting point machine.
T
Optical rotations [α] D were measured with a Perkin-Elmer 241 Polarimeter using a cell
with a pathlength of 0.25 dm. Concentrations (c) are given in grams per 100 ml.
Analytical TLC was carried out on pre-coated UV254 plates (Macherey-Nagel alugram.
Sil G/UV254 or Machery-Nagel polygram. Alox N/UV254), with visualisation by UV light at 254
nm, ninhydrin dip or potassium permanganate dip.
Flash column chromatography was carried out using Fluorochem Davisil 40 – 63 µm
6
0 Å silica, under a positive pressure by means of compressed air, followed by removal of the
solvent under reduced pressure after purification.
Enantiomeric ratios were determined by HPLC on a Hewlett-Packard system with UV
detection at 254 nm. A Chiralcel OD-H or Chiralpack AD-H column and hexane/2-propanol
as eluant were used for separations.
Reagents and solvents were purified by standard means. Tetrahydrofuran was distilled
from sodium wire and benzophenone under nitrogen. The Solvent Purification System (SPS)
was used for diethyl ether. Dichloromethane and diisopropylamide were obtained by
distillation from calcium hydride under nitrogen. Triethylamine was stored over potassium
hydroxide.
n-Butyllithium was obtained as a solution in hexanes and s-Butyllithium was in
cyclohexane. All the above organolithium solutions were titrated prior to use against a
solution of N-benzylbenzamide. Cooling baths used are acetone/dry ice for -78 °C and
acetonitrile/dry ice for -42 °C.
All reactions were conducted under an atmosphere of dry nitrogen in oven dried
glassware.
2
. Experimental procedures
2
.1 Preparation of the starting materials.
2

[
1]
General procedure A – Preparation of aryl amine by reductive amination.
H
N
NH2
O
"
NaBH(OAc)3"
R
R
Me
Me
AcOH, DCE
r.t.,4 h.
A two-necked round bottomed flame-dried flask was equipped with a magnetic stirring bar, a
nitrogen inlet, and a digital thermometer probe and was purged with nitrogen. The flask was
then charged with sodium borohydride (1.5 equiv.) and 1,2-dichloroethane (0.3M), then was
cooled to 0°C. Glacial acetic acid (4.5 equiv.) was added dropwise maintaining the internal
temperature of the flask below 5°C and upon completion of acid addition was allowed to
further react at 0°C for 45 min. to ensure completion of formation of sodium
triacetoxyborohydride. The flask was then brought to room temperature over the course of 30
min.. Amine (1.0 equiv.) and glacial acetic acid (1.5 equiv.) were added to the flask and
allowed to stir for 5 min., then distilled acetone (1.0 equiv.) was added to the flask dropwise.
The reaction mixture was further agitated at room temperature for a period of 4 h. The
reaction was quenched by the slow addition of saturated NaHCO and extracted into EtOAc 4
3
times. The resulting organic layers were combined, dried over anhydrous MgSO , filtered and
4
concentrated in vaccuo and the resulting crude was purified by flash column chromatography.
[
2]
General procedure B – Preparation of carbamoyl chlorides.
O
H
N
Cl CO
3
OCCl3
N
Cl
R
R
O
Py, CH Cl2
2
RT., 2 h.
To triphosgene (1.0 equiv.) in anhydrous CH Cl (0.3M) at -78°C were added pyridine (2.8
2
2
equiv.) then amine (2.8 equiv.) slowly. The reaction mixture was warmed to room
temperature, stirred for 2 h. then hydrolyzed with 1N HCl. The product was extracted with
CH Cl and the organic extract was washed with aqueous NaHCO , dried over MgSO and
2
2
3
4
concentracted in vaccuo. The resulted product was reacted on without purification.
[
3]
General procedure C – Preparation of α-aryl-O-vinylcarbamates.
3

N
Cl
N
O
O
O
R2
O
Me
R2
R1
DMSO, NaH,
RT, 15 h.
R1
A two-necked round bottomed flame-dried flask was equipped with a magnetic stirring bar, a
nitrogen inlet, and a digital thermometer probe and was purged with nitrogen. The flask was
then charged with sodium hydride (60% in mineral oil, 1.5 equiv.) and dry DMSO (2.5M) was
slowly added under nitrogen atmosphere and under vigorous stirring. The mixture was heated
at 75°C for 45 min and cooled to room temperature. The completion of the reaction is shown
by the disappearance of sodium hydride and the cessation of hydrogen evolution. The final
solution was milky and grey-olive in colour. Ketone (1.0 equiv.) in dry DMSO (4M) was
added slowly to dimsyl anion solution, the addition being slightly exothermic and changing
the color of the solution. The solution was stirred for 15 min. at room temperature and then
cooled to 10°C. The addition of the corresponding carbamoyl chloride (1.1 equiv.) in dry
DMSO (0.1M) was carried out while maintaining the temperature at 10°C. After stirring 15 h.
at room temperature, the solution was carefully quenched with water, extracted with n-hexane
5
times and dried over MgSO . The solvent was removed in vaccuo and the residue was
4
purified by flash column chromatography or crystallisation.
[
4]
General procedure D – Preparation of simple O-vinylcarbamates.
N
Cl
R
N
O
O
OLi
n-BuLi
R
O
O
RT, 15h.
DMPU, 4h., RT
A solution of n-BuLi (1.5 equiv.) in anhydrous THF (1.3 M) was stirred at room temperature
overnight. The solution was then cooled to 0°C and the corresponding N-isopropyl-N-aryl
carbamoyl chloride (1.0 equiv.) in anhydrous DMPU (1.7 M) was added. The solution was
allowed to stir at room temperature for 4 h., which caused the color to change to red. The
reaction was quenched with a saturated aqueous solution of NH Cl and after extraction with
4
Et O, the organic layer was washed with water twice and dried over MgSO . After removal of
2
4
the solvent in vaccuo, the residue was purified by flash column chromatography.
4

General procedure E – α-iodonisation of simple O-vinylcarbamates.
1. t-BuLi, THF, -78°C
N
O
N
O
R
R
2. I , THF, RT
2
O
I
O
To a solution of O-vinylcarbamate (1.0 equiv.) in anhydrous THF (0.25 M) was added t-BuLi
1.1 equiv.) at -78°C under nitrogen atmosphere. The yellow solution was stirred for 1 h.. A
(
solution of I (3.0 equiv.) in anhydrous THF was added dropwise at -78°C and the resulting
2
solution was allowed to warm up to room temperature for 30 min., then diluted with EtOAc
and quenched with a solution of Na S O (25%). The organic layer was washed with brine,
2
2
5
dried over MgSO , filtered and concentrated in vaccuo. The residue was purified by flash
4
column chromatography.
[
5]
General procedure F – Preparation of
α-propargyl-O-vinylcarbamates.
H
R1
, NEt
3
N
O
N
O
R2
R2
O
O
I
CuI, Pd(PPh ) , RT
4
3
R1
To iodovinylcarbamate (1.0 equiv.) in NEt (0.25 M) were added the corresponding acetylene
3
(
1.2 equiv.), CuI (2 mol%) and Pd(PPh ) (1 mol%) under nitrogen atmosphere. The reaction
3 4
mixture was stirred for 15 h. at room temperature after which a saturated aqueous solution of
NH Cl was added. The aqueous layer was extracted with Et O. The organic layer was washed
4
2
with water twice, dried over MgSO , filtered and concentrated in vaccuo. The residue was
4
purified by flash column chromatography.
4
-Chloro-N-isopropylbenzenamine. General procedure A was followed. 4-Cloroaniline (1.0
g) gave after flash column chromatography (SiO , Petrol:EtOAc 2%)
2
H
N
b
the title compound (951 mg, 72 %) as a colourless oil.
a
1
R 0.38 (Petrol:EtOAc 8:2); H-NMR (400MHz, CDCl ) δ 7.10 (d, J =
Cl
b
f
3
8
1
2
1
.8 Hz, 2H(aro)), 6.49 (d, J = 8.8 Hz, 2H(aro)), 3.58 (sept, J = 6.3 Hz, 1H ), 3.44 (br s, 1H(-NH)),
(a)
1
3
.20 (d, J = 6.3 Hz, 6H ) ; C-NMR (125MHz, CDCl ) δ 146.1, 129.0, 121.4, 114.2, 44.4,
(b)
3
+
+
2.9 ; MS m/z (ES+) 170 (100%, M+H ); HMRS (ES+) calcd for C H N Cl (M+H ):
9
13
1
1
70.0731, found: 170.0727.
5

N-Isopropyl-4-methylbenzenamine. General procedure A was followed. p-Toluidine (3.0 g)
gave after flash column chromatography (SiO , Petrol:EtOAc 3%) the
2
H
N
b
title compound (3.6 g, 86 %) as an orange oil.
a
1
R 0.48 (Petrol:EtOAc 8:2); H-NMR (400MHz, CDCl ) δ 6.98 (d, J
f
3
b
c
=
8.2 Hz, 2H(aro)), 6.52 (d, J = 8.2 Hz, 2H(aro)), 3.60 (sept, J = 6.3 Hz,
1
3
1
H ), 3.31 (br s, 1H
), 2.24 (s, 3H ), 1.20 (d, J = 6.3 Hz, 6H ) ; C-NMR (100MHz,
(
a)
(-NH) (c) (b)
+
CDCl ) δ 145.2, 129.7, 126.2, 113.5, 44.5, 23.0, 20.3 ; MS m/z (ES+) 150 (100%, M+H );
3
+
HMRS (ES+) calcd for C H N (M+H ): 150.1277, found: 150.1274.
10
16
1
(
3-Trifluoromethyl)-N-isopropylbenzenamine. General procedure A was followed. 3-
Trifluoromethyl)aniline (1.0 g) gave after flash column
chromatography (SiO , Petrol:EtOAc 1%) the title compound (1.1 g,
(
H
N
b
F3C
2
a
8
7 %) as a colourless oil.
b
-1
1
R 0.68 (Petrol:EtOAc 8:2); IR ν
f
(neat/cm ) 3417 (N-H); H-
max
NMR (400MHz, CDCl ) δ 7.28 (2d, J = 7.8 Hz, 1H(aro)), 6.93 (d, J = 7.8 Hz, 1H(aro)), 6.81 (s,
3
1
3
1
H(aro)), 6.75 (d, J = 7.8 Hz, 1H(aro)), 3.72-3.65 (m, 2H(a)(-NH)), 1.27 (d, J = 5.9 Hz, 6H ) ; C-
(b)
2
1
NMR (100MHz, CDCl ) δ 147.6, 131.5 (q, J = 32 Hz, J ), 129.6, 124.0 (q, J = 270 Hz, J
C-
3
C-F
3
3
F), 116.0, 113.1 (q, J = 3.8 Hz, J ), 109.1 (q, J = 3.8 Hz, J ), 44.1, 22.7 ; MS m/z (ES+)
C-F
C-F
+
+
2
04 (100%, M+H ), (ES-) 202 (100%, M-H ).
N-Isopropyl-4-methoxybenzenamine. General procedure A was followed. p-Anisidine (3.0
g) gave after flash column chromatography (SiO , Petrol:EtOAc 5%)
2
H
N
b
the title compound (3.6 g, 90 %) as a yellow oil.
a
-
1
1
R 0.25 (Petrol:EtOAc 8:2); IR ν
(neat/cm ) 3381 (N-H); H-
MeO
c
b
f
max
NMR (400MHz, CDCl ) δ 6.78 (d, J = 8.9 Hz, 2H(aro)), 6.57 (d, J =
3
8
6
.9 Hz, 2H(aro)), 3.75 (s, 3H ), 3.54 (sept, J = 6.3 Hz, 1H ), 3.11 (br s, 1H(-NH)), 1.19 (d, J =
(c) (a)
13
.3 Hz, 6H ) ; C-NMR (100MHz, CDCl ) δ 151.8, 141.7, 114.8, 55.7, 45.1, 23.0 ; MS m/z
(b)
3
+
+
(
ES+) 166 (100%, M+H ); HMRS (ES+) calcd for C H N O (M+H ): 166.1227, found:
10 16 1 1
1
66.1228.
6

Isopropyl(phenyl) carbamic chloride 2a. General procedure B was followed. N-
isopropylaniline (1.4 mL) gave the title compound 2a (1.1 g, 60 %) as a
b
b
a
white solid.
N
Cl
-1
1
R 0.53 (Petrol:EtOAc 8:2); IR ν
f
(neat/cm ) 1736 (C=O); H NMR
max
O
(
400MHz, CDCl ) δ 7.44-7.40 (m, 3H(aro)), 7.17-7.14 (m, 2H(aro)), 4.69 (sept,
3
1
3
J = 6.8 Hz, 1H ), 1.16 (d, J = 6.8 Hz, 6H ); C NMR (100MHz, CDCl ) δ 148.9, 138.3,
(a)
(b)
3
+
1
30.0, 129.1, 128.8, 52.3, 20.9; MS m/z (ES+) 220 (100%, M+Na ).
(4-Chlorophenyl)(isopropyl) carbamic chloride 2b. General procedure B was followed. 4-
Chloro-N-isopropylbenzenamine (920 mg) gave the title compound 2b
b
b
a
(929 mg, 74 %) as a white solid.
N
Cl
1
m.p. 81-83°C; H-NMR (400MHz, CDCl ) δ 7.41 (d, J = 8.8 Hz,
3
O
Cl
2H(aro)), 7.09 (d, J = 8.8 Hz, 2H(aro)), 4.68 (sept, J = 6.3 Hz, 1H ), 1.15
(a)
1
3
(
d, J = 6.3 Hz, 6H ) ; C-NMR (100MHz, CDCl ) δ 148.7, 136.7,
(b) 3
+
1
34.9, 131.4, 129.4, 52.3, 20.9 ; MS m/z (ES+) 254 (60%, M+Na ).
Isopropyl(p-tolyl) carbamic chloride 2c. General procedure B was followed. N-Isopropyl-4-
methylbenzenamine (3.5 g) gave the title compound 2c (3.9 mg, 79 %)
b
b
a
as a white solid.
N
Cl
-1
R 0.66 (Petrol:EtOAc 8:2); m.p. 72-74°C; IR ν
f
(neat/cm ) 1716
max
O
1
c
(C=O); H-NMR (400MHz, CDCl ) δ 7.21 (d, J = 8.1 Hz, 2H(aro)), 7.02
3
(
d, J = 8.1 Hz, 2H(aro)), 4.66 (sept, J = 6.8 Hz, 1H ), 2.39 (s, 1H ),
(a) (c)
1
3
1
.15 (d, J = 6.8 Hz, 6H ) ; C-NMR (100MHz, CDCl ) δ 149.1, 138.8, 135.5, 129.7, 52.1,
(b) 3
+
2
1.1, 20.8 ; MS m/z (ES+) 234 (100%, M+Na ).
(3-Trifluoromethyl)phenyl)(isopropyl) carbamic chloride 2d. General procedure B was
followed. (3-Trifluoromethyl)-N-isopropylbenzenamine (1.0 g) gave
b
b
a
the title compound 2d (1.2 g, 97 %) as a white solid.
F3C
N
Cl
-1
1
m.p. 68-70°C; IR νmax (neat/cm ) 1753 (C=O); H-NMR (400MHz,
O
CDCl ) δ 7.68 (d, J = 7.8 Hz, 1H(aro)), 7.57 (t, J = 7.8 Hz, 1H(aro)), 7.42
3
(
s, 1H(aro)), 7.36 (d, J = 7.8 Hz, 1H(aro)), 4.68 (sept, J = 6.8 Hz, 1H ), 1.16 (d, J = 6.8 Hz,
(a)
1
3
2
6
H ) ; C-NMR (100MHz, CDCl ) δ 148.2, 138.8, 131.9, 130.8 (q, J = 32 Hz, J ), 129.8,
(b) 3 C-F
7

3
3
1
1
26.8 (q, J = 3.1 Hz, J ), 125.6 (q, J = 3.1 Hz, J ), 123.0 (q, J = 270 Hz, J ), 52.5,
C-F C-F C-F
+
2
0.7 ; MS m/z (ES+) 288 (30%, M+Na ).
Isopropyl(4-methoxyphenyl) carbamic chloride 2e. General procedure B was followed. N-
Isopropyl-4-methoxybenzenamine (3.5 g) gave the title compound 2e
b
b
a
(3.1 mg, 65 %) as a pale yellow solid.
N
Cl
-1
1
m.p. 81-83°C; IR νmax (neat/cm ) 1731 (C=O); H-NMR (400MHz,
O
CDCl ) δ 7.02 (d, J = 8.9 Hz, 2H(aro)), 6.91 (d, J = 8.9 Hz, 2H(aro)),
MeO
c
3
4
.66 (sept, J = 6.8 Hz, 1H ), 3.83 (s, 1H ), 1.14 (d, J = 6.8 Hz,
(a) (c)
1
3
6
H ) ; C-NMR (100MHz, CDCl ) δ 159.5, 149.4, 131.0, 130.8, 114.1, 55.4, 52.0, 20.9 ;
(b) 3
+
MS m/z (ES+) 250 (100%, M+Na ).
Vinyl isopropylphenylcarbamate 6a. General procedure D was followed. Isopropyl(phenyl)
carbamic chloride 2a (1.0 g) gave after flash column chromatography
d
d
c
(
SiO , Petrol:EtOAc 1%) the title compound 6a (803 mg, 75 %) as a
2
b
N
O
white solid.
R 0.41 (Petrol:EtOAc 8:2); m.p. 33-35°C; IR ν (neat/cm ) 1719
a
O
-1
f
max
1
(
C=O); H-NMR (400MHz, CDCl ) δ 7.42-7.26 (m, 4H(aro)(a)), 7.12 (d, J = 7.0 Hz, 2H(aro)),
3
5
.70 (br s, 1H ), 5.39 (br s, 1H ), 4.58 (sept, J = 6.8 Hz, 1H ), 1.15 (d, J = 6.8 Hz, 6H ) ;
(a) (a’) (c) (d)
1
3
C-NMR (100MHz, CDCl ) δ 142.3, 129.7, 128.7, 127.7, 95.4, 49.4, 21.1 ; MS m/z (ES+)
3
+
+
2
2
28 (100%, M+Na ); HMRS (ES+) calcd for C H O N Na (M+Na ): 228.0995, found:
12 15 2 1 1
28.0992.
Vinyl 4-chlorophenylisopropylcarbamate 6b. General procedure D was followed. (4-
Chlorophenyl)(isopropyl) carbamic chloride 2b (1.2 g) gave after
d
d
c
flash column chromatography (SiO , Petrol:EtOAc 1%) the title
2
b
N
O
compound 6b (850 mg, 67 %) as a pale yellow oil.
a
O
-1
1
Cl
R 0.35 (Petrol:EtOAc 8:2); IR ν (neat/cm ) 1715 (C=O); H-
f
max
NMR (400MHz, CDCl ) δ 7.36 (d, J = 8.5 Hz, 2H ), 7.17 (dd, J = 14.0, 6.0 Hz, 1H ), 7.05
3
(aro)
(a)
(
d, J = 8.5 Hz, 2H(aro)), 4.59 (sept, J = 6.8 Hz, 1H ), 4.51 (br s, 1H ), 4.38 (br s, 1H ), 1.13
(c) (b) (b’)
1
3
(
d, J = 6.8 Hz, 6H ) ; C-NMR (100MHz, CDCl ) δ 142.2, 133.6, 131.0, 129.0, 95.7, 49.4,
(d) 3
+
2
1.2 ; MS m/z (ES+) 262 (100%, M+Na ); HMRS (ES+) calcd for C H O N Na Cl
12 14 2 1 1
1
+
(
M+Na ): 262.0606, found: 262.0598.
8

Vinyl isopropyl-p-tolylcarbamate 6c. General procedure D was followed. Isopropyl(p-tolyl)
carbamic chloride 2c (250 mg) gave after flash column
d
d
c
chromatography (SiO , Petrol:EtOAc 2%) the title compound 6c
2
b
N
O
(148 mg, 57 %) as a colourless oil.
a
O
-1
1
e
R 0.48 (Petrol:EtOAc 8:2); IR ν (neat/cm ) 1713 (C=O); H-
f
max
NMR (400MHz, CDCl ) δ 7.18-7.16 (m, 3H(aro)(a)), 6.99 (d, J = 7.5 Hz, 2H(aro)), 4.58 (sept, J
3
=
6.8 Hz, 1H ), 4.48 (br s, 1H ), 4.34 (br s, 1H ), 2.38 (s, 3H ), 1.12 (d, J = 6.8 Hz,
(c) (b) (b’) (e)
1
3
6
H ) ; C-NMR (100MHz, CDCl ) δ 142.4, 137.5, 129.4, 95.4, 49.2, 24.3, 21.1; MS m/z
(d) 3
+
+
(
ES+) 242 (100%, M+Na ); HMRS (ES+) calcd for C H O N Na (M+Na ): 242.1152,
13 17 2 1 1
found: 242.1156.
Vinyl 3-(trifluoromethyl)phenylisopropylcarbamate 6d. General procedure D was
followed.
chloride 2c (1.0 g) gave after flash column chromatography
SiO , Petrol:EtOAc 2%) the title compound 6d (680 mg, 63 %)
(3-Trifluoromethyl)phenyl)(isopropyl)
carbamic
d
d
c
b
F3C
N
O
(
2
a
O
as a colourless oil.
-1
1
R 0.68 (Petrol:EtOAc 8:2); IR ν (neat/cm ) 1717 (C=O); H-NMR (400MHz, CDCl )
f
max
3
δ 7.62 (d, J = 7.9 Hz, 1H(aro)), 7.52 (t, J = 7.9 Hz, 1H(aro)), 7.39 (s, 1H(aro)), 7.32 (d, J = 7.9 Hz,
H(aro)), 7.18 (dd, J = 14.0, 6.2 Hz, 1H ), 4.61 (sept, J = 6.8 Hz, 1H ), 5.56 (br s, 1H ), 4.40
1
(a)
(c)
(b)
1
3
(
br s, 1H ), 1.15 (d, J = 6.8 Hz, 6H ) ; C-NMR (100MHz, CDCl ) δ 142.1, 138.3, 133.2,
(b’) (d) 3
2
3
1
1
1
31.4 (q, J = 32 Hz, J ), 129.4, 126.5 (q, J = 3.7 Hz, J ), 125.5 (q, J = 270 Hz, J ),
C-F C-F C-F
3
+
24.6 (q, J = 3.7 Hz, J ), 95.9, 49.7, 21.2 ; MS m/z (ES+) 296 (100%, M+Na ); HMRS
C-F
+
(
ES+) calcd for C H O N F (M+H ): 274.1050, found: 274.1051.
1
3
15
2
1 3
Vinyl isopropyl-4-methoxyphenylcarbamate 6e. General procedure D was followed.
Isopropyl(4-methoxyphenyl) carbamic chloride 2e (1.0 g)
d
d
c
gave after flash column chromatography (SiO , Petrol:EtOAc
2
b
N
O
2
%) the title compound 6e (707 mg, 69 %) as a colourless oil.
a
O
-1
MeO
e
R 0.52 (Petrol:EtOAc 8:2); IR ν (neat/cm ) 1712 (C=O);
f
max
1
H-NMR (400MHz, CDCl ) δ 7.16 (br dd, J = 13.0, 4.9 Hz,
3
1
H ), 7.00 (d, J = 8.8 Hz, 2H(aro)), 6.87 (d, J = 8.8 Hz, 2H(aro)), 4.58 (sept, J = 6.7 Hz, 1H(c)),
(a)
1
3
4
.46 (d, J = 13.0 Hz, 1H ), 4.30 (br s, 1H ), 3.80 (s, 3H ), 1.09 (d, J = 6.7 Hz, 6H ) ; C-
(
b)
(b’)
(e)
(d)
NMR (100MHz, CDCl ) δ 158.7, 152.7, 142.3, 130.6, 129.6, 113.7, 95.2, 55.2, 49.0, 20.9 ;
3
9

+
+
MS m/z (ES+) 258 (100%, M+Na ); HMRS (ES+) calcd for C H O N (M+H ): 236.1282,
1
3
18
3
1
found: 236.1288.
1
-Iodovinyl isopropylphenylcarbamate 7a. General procedure E was followed. Vinyl
isopropylphenylcarbamate 6a (500 mg) gave after flash column
c
c
b
chromatography (SiO , Petrol:EtOAc 5%) the title compound 7a (715
2
a
N
O
mg, 88 %) as a white solid.
O
I
1
R 0.40 (Petrol:EtOAc 8:2); m.p. 62-64°C; H-NMR (400MHz,
f
CDCl ) δ 7.42-7.26 (m, 3H(aro)), 7.12 (d, J = 7.0 Hz, 2H(aro)), 5.70 (br s, 1H ), 5.39 (br s,
3
(a)
1
3
1
H ), 4.58 (sept, J = 6.8 Hz, 1H ), 1.15 (d, J = 6.8 Hz, 6H ) ; C-NMR (100MHz, CDCl )
(a’) (b) (c) 3
+
δ 129.7, 128.9, 128.0, 118.0, 102.0, 50.1, 21.0 ; MS m/z (ES+) 354 (100%, M+Na ); HMRS
+
(
ES+) calcd for C H O N Na I (M+Na ): 353.9961, found: 353.9958.
1
2
14
2
1
1 1
1
-Iodovinyl 4-chlorophenylisopropylcarbamate 7b. General procedure E was followed.
Vinyl 4-chlorophenylisopropylcarbamate 6b (606 mg) gave after
c
c
b
flash column chromatography (SiO , Petrol:EtOAc 2%) the title
2
a
N
O
compound 7b (470 mg, 51 %) as a white solid.
O
I
-1
Cl
R 0.40 (Petrol:EtOAc 8:2); m.p. 108-110°C; IR ν (neat/cm )
f
max
1
1
2
6
2
715 (C=O); H-NMR (400MHz, CDCl ) δ 7.37 (d, J = 8.5 Hz, 2H(aro)), 7.06 (d, J = 8.5 Hz,
3
H(aro)), 5.71 (br s, 1H ), 5.41(br s, 1H ), 4.56 (sept, J = 6.8 Hz, 1H ), 1.14 (d, J = 6.8 Hz,
(a)
(a’)
(b)
1
3
H ) ; C-NMR (100MHz, CDCl ) δ 150.1, 135.5, 133.9, 131.0, 129.2, 118.2, 101.6, 50.0,
(c)
3
+
1.1 ; MS m/z (ES+) 388 (100%, M+Na ); HMRS (ES+) found: 387.9572.
1
-Iodovinyl isopropyl-p-tolylcarbamate 7c. General procedure E was followed. Vinyl
isopropyl-p-tolylcarbamate 6c (332 mg) gave after flash column
c
c
b
chromatography (SiO , Petrol:EtOAc 2%) the title compound
2
a
N
O
7
c (191 mg, 37 %) as a yellow solid.
O
I
-1
R 0.40 (Petrol:EtOAc 8:2); m.p. 92-94°C; IR ν (neat/cm )
f
max
d
1
1
729 (C=O); H-NMR (400MHz, CDCl ) δ 7.19 (d, J = 7.8 Hz,
3
2
H(aro)), 6.99 (d, J = 7.8 Hz, 2H(aro)), 5.69 (br s, 1H ), 5.38 (br s, 1H ), 4.57 (sept, J = 6.8 Hz,
(a) (a’)
+
1
H ), 2.38 (s, 3H ), 1.14 (d, J = 6.8 Hz, 6H ) ; MS m/z (ES+) 368 (100%, M+Na ); HMRS
(b)
(d)
(c)
+
(
ES+) calcd for C H O N Na I (M+Na ): 368.0119, found: 368.0117.
13 16 2 1 1 1
1
0

1
-Iodovinyl 3-(trifluoromethyl)phenylisopropylcarbamate 7d. General procedure E was
followed. Vinyl 3-(trifluoromethyl)phenylisopropylcarbamate
c
c
b
6
d (668 mg) gave after flash column chromatography (SiO2,
a
F3C
N
O
Petrol:EtOAc 3%) the title compound 7d (390 mg, 40 %) as a
O
I
white solid.
-1
1
R 0.50 (Petrol:EtOAc 8:2); m.p. 58-60°C; IR ν
f
(neat/cm ) 1722 (C=O); H-NMR
max
(
400MHz, CDCl ) δ 7.63 (d, J = 7.9 Hz, 1H(aro)), 7.54 (t, J = 7.9 Hz, 1H(aro)), 7.39 (s, 1H(aro)),
3
7
1
3
=
.33 (d, J = 7.9 Hz, 1H(aro)), 5.74 (br s, 1H ), 5.43 (br s, 1H ), 4.58 (sept, J = 6.8 Hz, 1H ),
(a)
(a’)
(b)
1
3
.17 (d, J = 6.8 Hz, 6H ) ; C-NMR (100MHz, CDCl ) δ 150.8, 137.9, 132.1, 131.2 (q, J =
(c)
3
2
3
1
2 Hz, J ), 129.6, 126.5 (q, J = 3.7 Hz, J ), 125.2 (q, J = 270 Hz, J , C-9), 124.9 (q, J
C-F
C-F
C-F
3
+
3.7 Hz, J ), 118.4, 101.2, 50.3, 21.1 ; MS m/z (ES+) 422 (100%, M+Na ); HMRS (ES+)
C-F
+
calcd for C H N O F Na I (M+Na ): 421.9835, found: 421.9824.
1
3
13
1
2
3
1 1
1
-Iodovinyl isopropyl-4-methoxyphenylcarbamate 7e. General procedure E was followed.
Vinyl isopropyl-4-methoxyphenylcarbamate 6e (1.0 g) gave
c
c
b
after flash column chromatography (SiO , Petrol:EtOAc 2%)
2
a
N
O
the title compound 7e (707 mg, 69 %) as a colourless oil.
O
I
-
1
MeO
d
R 0.52 (Petrol:EtOAc 8:2); IR ν
(neat/cm ) 1719 (C=O);
f
max
1
H-NMR (400MHz, CDCl ) δ 7.02 (d, J = 8.7 Hz, 2H(aro)), 6.89
3
(
d, J = 8.7 Hz, 2H(aro)), 5.69 (br s, 1H ), 5.38 (br s, 1H ), 4.58 (sept, J = 6.8 Hz, 1H ), 3.83
(a) (a’) (b)
1
3
(
s, 3H ), 1.12 (d, J = 6.8 Hz, 6H ) ; C-NMR (100MHz, CDCl ) δ 159.0, 151.5, 130.7,
(d) (c) 3
+
1
29.4, 118.0, 114.0, 102.3, 55.4, 49.8, 21.0 ; MS m/z (ES+) 384 (100%, M+Na ); HMRS
+
(
ES+) calcd for C H N O Na I (M+Na ): 384.0068, found: 384.0057.
1
3
16
1
3
1 1
1
-Phenylvinyl methylphenylcarbamate 3a. General procedure C was followed.
Acetophenone 1a (300 mg) gave after crystallisation in Et O/n-
2
a
O
hexane (2/4) the title compound 3a (288 mg, 46 %) as a white
N
O
solid.
-1
b
R 0.36 (Petrol:EtOAc 8:2); m.p. 57-60°C; IR ν
f
(neat/cm )
max
1
1
706 (C=O); H-NMR (400MHz, CDCl ) δ 7.43-7.29 (m, 10H ), 5.41 (br s, 1H ), 5.08 (br
3 (aro) (a)
1
3
s, 1H ), 3.39 (br s, 3H ) ; C-NMR (100MHz, CDCl ) δ 153.5, 153.2, 142.8, 134.8, 129.1,
(a’)
(b)
3
+
1
28.7, 128.4, 126.7, 126.1, 124.9, 101.6, 38.2 ; MS m/z (ES+) 276 (100%, M+Na ); HMRS
+
(
ES+) calcd for C H O N Na (M+Na ): 276.0995, found: 276.1003.
1
6
15
2
1
1
1
1

1
-Phenylvinyl isopropylphenylcarbamate 3b. General procedure C was followed.
Acetophenone 1a (500 mg) gave after flash column
a
O
chromatography (SiO , Petrol:EtOAc 5%) the title compound 3b
2
N
O
(722 mg, 62 %) as a white solid.
b c
-1
c
R 0.24 (Petrol:EtOAc 8:2); m.p. 75-77°C; IR ν
f
(neat/cm )
max
1
1
1
698 (C=O); H NMR (400MHz, CDCl ) δ 7.45-7.23 (m, 10H ), 5.35 (s, 1H ), 5.03 (s,
3
(aro)
(a)
1
3
H ), 4.63 (sept, J = 6.8 Hz, 1H ), 1.16 (d, J = 6.8 Hz, 6H ); C NMR (100MHz, CDCl )
(a’)
(b)
(c)
3
δ 153.2, 137.9, 135.1, 129.9, 128.9, 128.5, 128.3, 127.8, 124.8, 101.1, 49.3, 21.2 ; MS m/z
+
+
(
ES+) 304 (100%, M+Na ); HMRS (ES+) calcd for C H O N Na (M+Na ): 304.1308,
18 19 2 1 1
found: 304.1297.
1
-Phenylvinyl 4-chlorophenylisopropylcarbamate 3c. General procedure C was followed.
Acetophenone 1a (400 mg) gave after flash column
Cl
a
O
chromatography (SiO , Petrol:EtOAc 5%) the title compound
2
N
O
3
c (529 mg, 50 %) as a white solid.
b
c
c
-1
R 0.27 (Petrol:EtOAc 8:2); m.p. 95-97°C; IR ν (neat/cm )
f
max
1
1
7
1
1
698 (C=O); H NMR (400MHz, CDCl ) 7.41 (d, J = 8.5 Hz, 2H(aro)), 7.31-7.29 (m, 5H(aro)),
3
.18 (d, J = 8.5 Hz, 2H(aro)), 5.36 (br s, 1H ), 5.02 (br s, 1H ), 4.63 (sept, J = 6.6 Hz, 1H ),
(a)
(a’)
(b)
1
3
.15 (d, J = 6.6 Hz, 6H ); C NMR (100MHz, CDCl ) δ 153.2, 153.0, 136.4, 134.9, 133.7,
(c)
3
+
31.1, 129.2, 128.7, 128.3, 124.8, 101.4, 49.3, 21.2; MS m/z (ES+) 338 ((100%, M+Na );
+
HMRS (ES+) calcd for C H O N Cl Na (M+Na ): 338.0919, found: 338.0905.
18
18
2
1
1
1
1
-(4-Chlorophenyl)vinyl isopropylphenylcarbamate 3d. General procedure C was followed.
-Chloroacetophenone 1b (500 mg) gave after flash column
chromatography (SiO , Petrol:EtOAc 5%) the title compound
4
a
O
2
N
O
3
d (611 mg, 60 %) as a yellow solid.
Cl
c
b
c
-1
R 0.19 (Petrol:EtOAc 8:2); m.p. 82-84°C; IR ν (neat/cm )
f
max
1
1
717 (C=O); H NMR (400MHz, CDCl ) δ 7.46-7.36 (m, 3H(aro)), 7.26-7.21 (m, 6H(aro)), 5.31
3
1
3
(
s, 1H ), 5.06 (s, 1H ), 4.61 (sept, J = 4.0 Hz, 1H ), 1.15 (d, J = 4.0 Hz, 6H ); C NMR
(a) (a) (b) (c)
(
100MHz, CDCl ) δ 152.2, 137.8, 134.4, 133.7, 129.8, 129.0, 128.5, 127.9, 126.2, 101.5, 49.4,
3
+
2
1.2; MS m/z (ES+) 338 (100%, M+Na ); HMRS (ES+) calcd for C H O N Cl Na
18
18
2
1
1
1
+
(
M+Na ): 338.0918, found: 338.0908.
1
2

1
-(4-Methoxyphenyl)vinyl isopropylphenylcarbamate 3e. General procedure C was
followed. p-Methoxyacetophenone 1c (500 mg) gave after
b
O
flash column chromatography (SiO , Petrol:EtOAc 10%)
2
N
O
the title compound 3e (370 mg, 37 %) as a white solid.
c
OMe
a
1
d
R 0.17 (Petrol:EtOAc 8:2); m.p. 81-83°C; H NMR
f
d
(
400MHz, CDCl ) δ 7.43-7.22 (m, 7H(aro)), 6.81 (d, J = 8.4
3
Hz, 2H(aro)), 5.22 (s, 1H ), 4.93 (s, 1H ), 4.63 (sept, J = 6.8 Hz, 1H ), 3.79 (s, 3H ), 1.15
(b)
(b’)
(c)
(a)
1
3
(
d, J = 6.8 Hz, 6H ); C NMR (100MHz, CDCl ) δ 159.8, 153.1, 138.0, 129.9, 128.9, 127.8,
(d) 3
+
1
27.7, 126.2, 113.7, 99.3, 55.3, 49.2, 21.2; MS m/z (ES+) 334 ((100%, M+Na ); HMRS (ES+)
+
calcd for C H O N Na (M+Na ): 334.1414, found: 334.1415.
1
8
21
3
1
1
(Z)-1-Phenylprop-1-enyl methylphenylcarbamate 3f. The procedure C was followed.
Propiophenone 1d (500 mg) gave after flash column
a
b
chromatography (SiO , Petrol:EtOAc 5%) the title compound 3f
2
O
(568 mg, 57 %) as a white solid.
N
O
1
R 0.20 (Petrol:EtOAc 8:2); m.p. 53-55°C; H NMR (400MHz,
c
f
CDCl ) δ 7.44-7.22 (m, 10H ), 5.83 (q, J = 6.8 Hz, 1H ), 3.40 (br s, 3H ), 1.75 (d, J = 6.8
3
(aro)
(b)
(c)
1
3
Hz, 3H ); C NMR (100MHz, CDCl ) δ 153.2, 147.3, 143.0, 135.6, 129.1, 128.4, 127.8,
(a)
3
+
1
26.3, 126.0, 124.3, 112.7, 38.3, 11.5; MS m/z (ES+) 290 (100%, M+Na ); HMRS (ES+)
+
calcd for C H O N Na (M+Na ): 290.1152, found: 290.1145. The stereochemistry was
1
7
17
2
1
1
deduced by NOE experiment.
(Z)-1,2-Diphenylvinyl isopropylphenylcarbamate 3g. General procedure C was followed.
Deoxybenzoin 1e (500 mg) gave after flash column
chromatography (SiO , Petrol:EtOAc 5%) the title compound 3g
2
a
O
(485 mg, 55 %) as a white solid.
N
O
-1
R 0.38 (Petrol:EtOAc 8:2); m.p. 96-98°C; IR ν
f
(neat/cm )
max
b
1
c
c
1
716 (C=O); H NMR (400MHz, CDCl ) δ 7.51-7.23 (m,
3
1
3
1
5H(aro)), 6.56 (s, 1H ), 4.57 (sept, J = 6.6 Hz, 1H ), 1.11 (d, J = 6.6 Hz, 6H ); C NMR
(a) (b) (c)
(
100MHz, CDCl ) δ 152.1, 147.0, 137.6, 136.5, 134.5, 129.9, 128.9, 128.8, 128.5, 128.2,
3
+
1
28.1, 128.0, 127.2, 124.7, 116.6, 49.3, 21.1; MS m/z (ES+) 380 (100%, M+Na ); HMRS
+
(
ES+) calcd for C H O N Na (M+Na ): 380.1621, found: 380.1625.
2
4
23
2
1
1
1
3

The Z-stereochemistry was deduced by an X-ray crystal structure:
(Z)-1,2-diphenylvinyl 4-chlorophenylisopropylcarbamate 3h. General procedure C was
followed. Deoxybenzoin 1e (1.10 g) gave after flash column
chromatography (SiO , Petrol:EtOAc 5%) the title compound
2
Cl
a
O
3
h (1.1 g, 46 %) as a white solid.
N
O
-1
R 0.45 (Petrol:EtOAc 8:2); m.p. 83-85°C; IR ν (neat/cm )
f
max
b
1
c
c
1
718 (C=O); H NMR (400MHz, CDCl ) δ 7.47-7.20 (m,
3
1
3
1
4H(aro)), 6.58 (s, 1H ), 4.56 (sept, J = 6.3 Hz, 1H ), 1.09 (d, J = 6.3 Hz, 6H ); C NMR
(a) (b) (c)
(
100MHz, CDCl ) δ 151.9, 146.9, 136.2, 134.4, 134.0, 131.2, 131.1, 129.2, 128.8, 128.5,
3
+
1
28.5, 128.4, 128.2, 127.3, 124.6, 116.7, 49.2, 21.1 ; MS m/z (ES+) 414 (100%, M+Na );
+
HMRS (ES+) calcd for C H O N Na (M+Na ): 414.1231, found: 414.1231.
24
22
2
1
1
5
,5-Dimethylhex-1-en-3-yn-2-yl isopropylphenylcarbamate 8a. General procedure F was
followed. 1-Iodovinyl isopropylphenylcarbamate 7a (710 mg)
a
O
gave after flash column chromatography (SiO , Petrol:EtOAc
2
N
O
d
2% then 4%) the title compound 8a (533 mg, 87 %) as a white
b
d
solid.
c
c
d
-1
R 0.56 (Petrol:EtOAc 8:2); m.p. 68-70°C; IR ν (neat/cm )
f
max
1
2
7
9
1
211 (C≡C), 1712 (C=O); H-NMR (400MHz, CDCl ) δ 7.39-7.30 (m, 3H(aro)), 7.13 (d, J =
3
.0 Hz, 2H(aro)), 5.04 (br s, 1H ), 4.99 (br, s, 1H ), 4.59 (sept, J = 6.8 Hz, 1H ), 1.24 (s,
(a)
(a’)
(b)
1
3
H ), 1.14 (d, J = 6.8 Hz, 6H ); C-NMR (100MHz, CDCl ) δ 152.8, 138.0, 137.1, 129.7,
(d)
(c)
3
+
28.7, 127.5, 109.2, 98.4, 73.8, 49.6, 30.5, 27.7, 21.2 ; MS m/z (ES+) 308 (100%, M+Na );
+
HMRS (ES+) calcd for C H O N Na (M+Na ): 308.1621, found: 308.1623.
18
23
2
1
1
1
4

5
,5-Dimethylhex-1-en-3-yn-2-yl
4-chlorophenylisopropylcarbamate
procedure was followed.
8b.
General
4-
F
1-Iodovinyl
Cl
a
O
chlorophenylisopropylcarbamate 7b (470 mg) gave after
N
O
d
flash column chromatography (SiO , Petrol:EtOAc 2%
2
b
then 3%) the title compound 8b (302 mg, 74 %) as a
c
c
d
d
white solid.
-1
1
R 0.40 (Petrol:EtOAc 8:2); m.p. 75-77°C; IR ν (neat/cm ) 2209 (C≡C), 1702 (C=O); H-
f
max
NMR (400MHz, CDCl ) δ 7.34 (d, J = 8.8 Hz, 2H(aro)), 7.07 (d, J = 8.8 Hz, 2H(aro)), 5.06 (br s,
3
1
6
7
H ), 4.99 (br, s, 1H ), 4.58 (sept, J = 6.8 Hz, 1H ), 1.24 (s, 9H ), 1.38 (d, J = 6.8 Hz,
(a) (a’) (b) (d)
1
3
H ); C-NMR (100MHz, CDCl ) δ 152.5, 137.0, 136.5, 133.4, 131.0, 129.0, 109.3, 98.6,
(c)
3
+
3.6, 49.5, 30.5, 27.7, 21.2 ; MS m/z (ES+) 342 (100%, M+Na ); HMRS (ES+) calcd for
+
C H O N Na Cl (M+Na ): 342.1232, found: 342.1233.
18
22
2
1
1
1
5
,5-Dimethyl-1-en-3-yn-2-yl isopropyl-p-tolylcarbamate 8c. General procedure F was
followed. 1-Iodovinyl isopropyl-p-tolylcarbamate 7c (184
e
a
O
mg) gave after flash column chromatography (SiO2,
N
O
d
Petrol:EtOAc 5%) the title compound 8c (112 mg, 70 %)
as a white solid.
b
c
c
d
d
R 0.33 (Petrol:EtOAc 8:2); m.p. 45-47°C; IR ν
f
max
-1
1
(
neat/cm ) 2215 (C≡C), 1720 (C=O); H-NMR (400MHz, CDCl ) δ 7.17 (d, J = 8.0 Hz,
3
2
H(aro)), 7.00 (d, J = 8.0 Hz, 2H(aro)), 5.04 (br s, 1H ), 4.98 (br, s, 1H ), 4.58 (sept, J = 6.8
(a) (a’)
1
3
Hz, 1H ), 2.37 (s, 1H ), 1.24 (s, 9H ), 1.12 (d, J = 6.8 Hz, 6H ); C-NMR (100MHz,
(b)
(e)
(d)
(c)
CDCl ) δ 153.2, 137.3, 137.2, 129.4, 129.3, 109.2, 98.3, 73.9, 49.4, 30.5, 27.7, 21.2, 21.1 ;
3
+
+
MS m/z (ES+) 322 (100%, M+Na ); HMRS (ES+) calcd for C H O N Na (M+Na ):
1
9
25
2
1
1
3
22.1778, found: 322.1772.
5
,5-Dimethyl-1-en-3-yn-2-yl 3-(trifluoromethyl)phenylisopropylcarbamate 8d. General
procedure was followed. 1-Iodovinyl 3-
trifluoromethyl)phenylisopropylcarbamate 7d (369
F
a
O
(
F3C
N
O
d
mg) gave after flash column chromatography (SiO2,
Petrol:EtOAc 2% then 4%) the title compound 8d (245
mg, 75 %) as a yellow oil.
b
c
c
d
d
1
5

-1
1
R 0.61 (Petrol:EtOAc 8:2); IR ν
f
(neat/cm ) 2216 (C≡C), 1725 (C=O); H-NMR
max
(
400MHz, CDCl ) δ 7.60 (d, J = 7.8 Hz, 1H(aro)), 7.52 (t, J = 7.8 Hz, 1H(aro)), 7.40 (s, H(aro)),
3
7
1
1
.33 (d, J = 7.8 Hz, 1H(aro)), 5.07 (br s, 1H ), 5.01 (br, s, 1H ), 4.60 (sept, J = 6.8 Hz, 1H ),
(a)
(a’)
(b)
1
3
.24 (s, 9H ), 1.16 (d, J = 6.8 Hz, 6H ); C-NMR (100MHz, CDCl ) δ 152.4, 138.8, 136.9,
(d)
(c)
3
2
3
1
33.1, 131.4 (q, J = 32 Hz, J ), 129.4, 126.5 (q, J = 3.7 Hz, J ), 127.0 (q, J = 270 Hz, J
C-
C-F
C-F
3
F), 124.4 (q, J = 3.7 Hz, J ), 109.4, 98.8, 73.5, 49.9, 30.4, 27.7, 21.2 ; MS m/z (ES+) 376
C-F
+
+
(
100%, M+Na ); HMRS (ES+) calcd for C H O N F Na (M+Na ): 376.1495, found:
19 22 2 1 3 1
3
76.1487.
5
,5-Dimethylhex-1-en-3-yn-2-yl isopropyl-4-methoxyphenylcarbamate 8e. General
procedure F was followed. 1-Iodovinyl isopropyl-4-
MeO
e
a
O
methoxyphenylcarbamate 7e (506 mg) gave after flash
N
O
column chromatography (SiO , Petrol:EtOAc 5%) the
d
2
b
title compound 8e (325 mg, 74 %) as an orange oil.
c
c
d
d
-1
R 0.64 (Petrol:EtOAc 8:2); IR ν
f
(neat/cm ) 2215
max
1
(
C≡C), 1719 (C=O); H-NMR (400MHz, CDCl ) δ 7.01 (d, J = 8.9 Hz, 2H(aro)), 6.88 (d, J =
3
8
3
1
.9 Hz, 2H(aro)), 5.03 (br s, 1H ), 4.96 (br, s, 1H ), 4.58 (sept, J = 6.8 Hz, 1H ), 3.82 (s,
(a) (a’) (b)
1
3
H ), 1.24 (s, 9H ), 1.11 (d, J = 6.8 Hz, 6H ); C-NMR (100MHz, CDCl ) δ 158.7, 152.9,
(e)
(d)
(c)
3
37.2, 130.7, 113.9, 109.2, 98.3, 73.9, 55.3, 49.2, 30.5, 27.7, 21.1 ; MS m/z (ES+) 338 (100%,
+
+
M+Na ); HMRS (ES+) calcd for C H O N Na (M+Na ): 338.1727, found: 338.1729.
1
9
25
3
1
1
4
-(Triisopropylsilyl)but-1-en-3-yn-2-yl isopropylphenylcarbamate 8f. General procedure
F was followed. 1-Iodovinyl isopropylphenylcarbamate 7a
a
O
(416 mg) gave after flash column chromatography (SiO2,
Petrol:EtOAc 2%) the title compound 8f (363 mg, 75 %) as
a colourless oil.
N
O
Si(i-Pr)3
d
b
c
c
-1
R 0.63 (Petrol:EtOAc 8:2); IR ν (neat/cm ) 1725 (C=O);
f
max
1
H-NMR (400MHz, CDCl ) δ 7.37-7.30 (m, 3H(aro)), 7.12 (d, J = 9.6 Hz, 2H(aro)), 5.17 (br s,
3
1
H ), 5.10 (br, s, 1H ), 4.58 (sept, J = 6.8 Hz, 1H ), 1.13 (d, J = 6.8 Hz, 6H ), 1.09 (s,
(a) (a’) (b) (c)
1
3
2
1H ); C-NMR (100MHz, CDCl ) δ 152.5, 138.0, 136.6, 129.7, 128.7, 127.6, 110.6, 100.6,
(d) 3
+
9
1.6, 49.7, 21.1, 18.5, 11.1 ; MS m/z (ES+) 408 (100%, M+Na ); HMRS (ES+) calcd for
+
C H O N Si (M+H ): 386.2510, found: 386.2506.
23
36
2
1
1
1
6

4
-(Trimethylsilyl)but-1-en-3-yn-2-yl isopropylphenylcarbamate 8g. General procedure F
was followed. 1-Iodovinyl isopropylphenylcarbamate 7a
a
O
(596 mg) gave after flash column chromatography (SiO2,
N
O
Petrol:EtOAc 2%) the title compound 8g (402 mg, 74 %) as
Si(Me)3
d
b
a white solid.
c
c
-1
1
R 0.39 (Petrol:EtOAc 8:2); m.p. 73-75 °C; IR ν (neat/cm ) 2166 (C≡C), 1714 (C=O); H-
f
max
NMR (400MHz, CDCl ) δ 7.40-7.31 (m, 3H(aro)), 7.14 (d, J = 7.2 Hz, 2H(aro)), 5.20 (br s,
3
1
9
9
H ), 5.10 (br, s, 1H ), 4.59 (sept, J = 6.8 Hz, 1H ), 1.14 (d, J = 6.8 Hz, 6H ), 0.20 (s,
(a) (a’) (b) (c)
1
3
H ); C-NMR (100MHz, CDCl ) δ 152.6, 137.8, 136.6, 129.7, 128.7, 127.6, 111.5, 98.5,
(d)
3
+
5.0, 49.7, 21.2, -0.40 ; MS m/z (ES+) 324 (100%, M+Na ).
4
-Phenylbut-1-en-3-yn-2-yl isopropylphenylcarbamate 8h. General procedure F was
followed. 1-Iodovinyl isopropylphenylcarbamate 7a (394 mg)
a
O
gave after flash column chromatography (SiO , Petrol:EtOAc
2
N
O
1
%) the title compound 8h (293 mg, 81 %) as a white solid.
b
-1
c
c
R 0.36 (Petrol:EtOAc 8:2); m.p. 75-77°C; IR ν (neat/cm )
f
max
1
2
207 (C≡C), 1713 (C=O); H-NMR (400MHz, CDCl )
3
δ 7.48-7.30 (m, 8H(aro)), 7.18 (d, 2H(aro), J = 7.0 Hz), 5.27 (br s, 1H ), 5.17 (br, s, 1H ), 4.63
(a)
(a’)
1
3
(
sept, J = 6.8 Hz, 1H ), 1.16 (d, J = 6.8 Hz, 6H ); C-NMR (100MHz, CDCl ) δ 152.7,
(b) (c) 3
1
37.8, 136.8, 131.8, 129.7, 128.9, 128.8, 127.7, 122.0, 111.2, 89.0, 83.6, 49.6, 21.2 ; MS m/z
+
+
(
ES+) 328 (100%, M+Na ); HMRS (ES+) calcd for C H O N Na (M+Na ): 328.1308,
20 19 2 1 1
found: 328.1307.
(E)-4-Phenylbuta-1,3-dien-2-yl isopropylphenylcarbamate 9. To a solution of vinyl
isopropylphenylcarbamate 6a (200 mg) in anhydrous THF (4
mL) was added t-BuLi (1.1 equiv., 0.56 mL) at -78°C. After
1h., a solution of ZnCl (1.0 M in Et O, 1.1 equiv., 1.1 mL)
c
O
a
N
O
b
2
2
e d
e
was added dropwise. The mixture was stirred for an
additional 30 min. at -78°C then at 0°C for 45 min. The resulting solution was transferred to a
flask containing bromostyrene (1.1 equiv., 0.14 mL) and Pd(PPh ) (5 mol%, 60 mg) in THF
3
4
(4 mL) and it was stirred at room temperature for 4h. The reaction was then quenched with a
saturated aqueous solution of NH Cl, extracted with ether twice and the combined organic
4
layers were washed with water, brine and dried over MgSO . The residue was purified by
4
1
7

flash column chromatography (SiO , Petrol:EtOAc 5%) to afford the title compound 9 (210
2
mg, 70 %) as a pale yellow solid.
-1
1
R 0.55 (Petrol:EtOAc 8:2); m.p. 71-73°C; IR ν
f
(neat/cm ) 1720 (C=O); H-NMR
max
(
400MHz, CDCl ) δ 7.48-7.22 (m, 10H(aro)), 6.51 (d, J = 15.8 Hz, 1H ), 6.27 (br s, 1H ),
3 (b) (a)
1
3
5
.13 (s, 1H ), 4.97 (s, 1H ), 4.68 (sept, J = 6.8 Hz, 1H ), 1.18 (d, J = 6.8 Hz, 6H ) ; C-
(c)
(c’)
(d)
(e)
NMR (100MHz, CDCl ) δ 152.6, 151.8, 137.8, 136.1, 129.8, 129.3, 128.9, 127.9, 126.6,
3
+
1
23.4, 104.5, 49.1, 21.1 ; MS m/z (ES+) 330 (100%, M+Na ); HMRS (ES+) calcd for
+
C H O N Na (M+Na ): 330.1465, found: 330.1470.
20
21
2
1
1
1
-(Dimethyl(phenyl)silyl)vinyl isopropylphenylcarbamate 10. To a solution of vinyl
isopropylphenylcarbamate 6a (170 mg) in dry THF (3 mL) was
a
O
added t-BuLi (1.1 equiv.) at -78°C under nitrogen atmosphere.
N
O
SiMe Ph
2
The mixture was stirred for 1 h. at -78°C after which
d
b
PhMe SiCl (1.2 equiv., 0.17 mL) was added. The reaction was
2
c
c
stirred at -78°C for 15 min. and then at room temperature for 2
h.. A solution of saturated NH Cl was added and the reaction mixture stirred for a further 30
4
min. while warming to room temperature. The mixture was partitioned between diethyl ethyl
ether and water. The organic layer was washed with water and the organic layer was dried
over MgSO and concentrated in vaccuo to give a residue which was purified by flash column
4
chromatography (SiO , Petrol:EtOAc 1%) to give the title compound 10 (145 mg, 52 %) as a
2
colourless oil.
1
R 0.67 (Petrol:EtOAc 8:2); H-NMR (400MHz, CDCl ) δ 7.50 (d, J = 7.2 Hz, 2H(aro)), 7.35-
f
3
7
.29 (m, 6H(aro)), 6.90 (d, J = 7.2 Hz, 2H(aro)), 5.44 (br s, 1H ), 5.01 (br s, 1H ), 4.47 (sept, J
(a) (a’)
1
3
=
6.8 Hz, 1H ), 1.01 (d, J = 6.8 Hz, 6H ), 0.41 (s, 6H ) ; C-NMR (100MHz, CDCl )
(b) (c) (d) 3
δ 162.0, 138.0, 136.9, 134.1, 129.8, 129.1, 128.6, 127.6, 127.4, 115.0, 48.9, 21.1, -2.30 ; MS
+
m/z (ES+) 362 (100%, M+Na ).
2
.2 Carbolithiation and N→C aryl migration of O-vinylcarbamates.
General procedure G – Alkylation/arylation reactions in THF or THF/DMPU.
A solution of organolithium (2.0 equiv.) was added dropwise to a precooled solution (-78 °C
or -45°C) of carbamate (1.0 equiv.) in anhydrous THF (0.15 M) or in a mixture of anhydrous
THF and DMPU (4:1, 0.13 M). The resulting reaction mixture was stirred at -78°C or -45°C
1
8

under nitrogen atmosphere after which MeOH and a saturated solution of NH Cl were added
4
and the reaction mixture stirred for a further 30 min. while warming to room temperature. The
mixture was partitioned between diethyl ether and water. The organic layer was washed 3
times with water and the combined organic layers were dried over MgSO and concentrated in
4
vaccuo to give a residue which was purified by flash column chromatography or by
recrystallisation.
General procedure H – Alkylation/arylation reactions and quenching with t-BuONO.
A solution of organolithium (2.0 equiv.) was added dropwise to a precooled solution (-78 °C)
of carbamate (1.0 equiv.) in a mixture of anhydrous THF and DMPU (4:1, 0.15 M). The
resulting reaction mixture was stirred at -78°C under nitrogen atmosphere after which tert-
butyl nitrite (6.0 equiv.) was added and the reaction mixture stirred overnight. The mixture
was partitioned between diethyl ether and a saturated aqueous solution of K CO . The organic
2
3
layer was washed 3 times with saturated aqueous K CO , dried over MgSO , filtered and
2
3
4
concentrated in vaccuo to give a residue which was purified by flash column chromatography.
General procedure I – Alkylation/arylation reactions in toluene/TMEDA.
A solution of n-BuLi (2.5 equiv.) was added dropwise to a precooled solution (-78 °C) of
vinylcarbamate (1.0 equiv.) in a mixture of anhydrous toluene (0.14 M) and distilled TMEDA
(2.5 equiv.) under nitrogen atmosphere. The resulting reaction mixture was warmed up to -
3
0°C for 2 h. after which MeOH and a saturated solution of NH Cl were added and the
4
reaction mixture stirred for a further 30 min. while warming to room temperature. The
mixture was partitioned between diethyl ether and water. The organic layer was washed with
a solution of CuSO and water twice and the combined organic layers were dried over MgSO4
4
and concentrated in vaccuo. The residue was purified by flash column chromatography.
General procedure J – Alkylation/arylation reactions in toluene/TMEDA followed by
addition of DMPU.
A solution of n-BuLi (2.5 equiv.) was added dropwise to a precooled solution (-78 °C) of
vinylcarbamate (1.0 equiv., 50 mg) in a mixture of anhydrous toluene (0.14 M) and distilled
TMEDA (2.5 equiv.) under nitrogen atmosphere. The resulting reaction mixture was warmed
up to -30°C for 2 h. after which anhydrous DMPU (0.25 mL) was added and stirred for 15 h..
The reaction was quenched with MeOH and a saturated solution of NH Cl stirred for a further
4
3
0 min. while warming to room temperature. The mixture was partitioned between diethyl
1
9

ether and water. The organic layer was washed with a solution of CuSO and water twice and
4
the combined organic layers were dried over MgSO and concentrated in vaccuo. The residue
4
was purified by flash column chromatography.
3
-Methyl-1,1-diphenylbutyl methylcarbamate 11. General procedure G was followed. 1-
Phenylvinyl methylphenylcarbamate 3a (50 mg) gave after flash
c
b
column chromatography (SiO , Petrol:EtOAc 2%) the title
2
O
a
c
compound 11 (21 mg, 36%) as a colourless oil.
MeHN
d
O
-1
R 0.52 (Petrol:EtOAc 8:2); IR ν (neat/cm ) 3390 (N-H), 1627
f
max
1
(
C=O); H NMR (400MHz, CDCl ) δ 7.41-7.03 (br m, 10H(aro)),
3
5
.11 (br s, 1H(-NH)), 3.20 (br s, 3H ), 2.09-1.83 (br m, 3H(a)(b)), 1.01
(d)
1
3
(
t, J = 5.9 Hz, 6H ); C NMR (100MHz, CDCl ) δ 174.8, 143.9, 128.8, 128.1, 127.6, 127.3,
(c) 3
+
1
25.8, 78.0, 44.6, 40.8, 24.4, 24.1; MS m/z (ES+) 298 (100%, M+H ); HMRS (ES+) calcd
+
for C H O N (M+H ): 298.1802, found: 298.1806.
1
9
24
2
1
3
-Methyl-1,1-diphenylbutyl isopropylcarbamate 12. General procedure was G followed. 1-
Phenylvinyl isopropylphenylcarbamate 3b (50 mg) gave after
c
b
recrystallisation in Hexane:Et O (9:1) the title compound 13 (46 mg,
2
e
a
O
c
d
80%) as a white solid.
N
H
O
e
-1
R 0.58 (Petrol:EtOAc 8:2); m.p. 154-156°C; IR ν
f
(neat/cm )
max
1
1
687 (C=O); H NMR (400MHz, CDCl ) δ 7.34 (d, J = 7.6 Hz,
3
4
H(aro)), 7.26 (t, J = 7.2 Hz, 4H(aro)), 7.17 (t, J = 7.2 Hz, 2H(aro)), 4.68 (br d, J = 7.2 Hz, 1H(-
NH)), 3.70 (sept, J = 6.4 Hz, 1H ), 2.74 (d, J = 5.6 Hz, 2H ), 1.56-1.48 (m, 1H ), 1.11 (d, J
(d)
(a)
(b)
1
3
=
6.4 Hz, 6H ), 0.81 (d, J = 6.4 Hz, 6H ); C NMR (100MHz, CDCl ) δ 153.5, 146.0,
(e) (c) 3
+
1
27.9, 126.5, 125.8, 85.3, 44.7, 42.6, 24.0, 23.8, 23.0; MS m/z (ES+) 298 (100%, M+Na );
+
HMRS (ES+) calcd for C H O N (M+Na ): 298.1802, found: 298.1806.
19
24
2
1
1
,1-Diphenylhexan-1-ol 14a. General procedure H was followed. 1-Phenylvinyl
isopropylphenylcarbamate 3b (50 mg) gave after flash column
e
d
chromatography (SiO , Petrol:EtOAc 1%) the title compound 14a (25
2
c
b
mg, 57 %) as a colourless oil.
a
OH
1
R 0.61 (Petrol:EtOAc 8:2); H NMR (400MHz, CDCl ) δ 7.43-7.20
f
3
(
m, 10H(aro)), 2.29-2.25 (m, 2H ), 2.09 (s, 1H(-OH)), 1.30-1.27 (m,
(a)
2
0

1
3
6
H(b)(c)(d)), 0.85 (t, J = 6.8 Hz, 3H ); C NMR (125MHz, CDCl ) δ 147.2, 128.1, 126.7,
(e) 3
+
1
26.0, 78.3, 41.9, 32.2, 23.4, 22.5, 14.0; MS m/z (ES-) 254 (100%, M ); HMRS (ES+) calcd
+
for C H O (M ): 254.1665, found: 254.1665; MS (EI) 183 (M-C H ).
1
8
22
1
5
11
1
,1,3-Triphenylpropan-1-ol 14d. To a mixture of anhydrous toluene (0.1 mL) and distilled
−)-sparteine (0.10 mL, 2.5 equiv.) was added sec-BuLi( 1.20 M, 2.4
(
equiv, 0.35 mL) at -45°C under nitrogen atmosphere, then the mixture
reaction was stirred at room temperature for 1 h.. To a solution of 1-
phenylvinyl isopropylphenylcarbamate 3b (50 mg) in anhydrous THF
OH
(1 mL) and DMPU (0.25 mL) was added the above yellow solution
dropwise at -78°C under nitrogen atmosphere. The resulting reaction
mixture was stirred at -78°C under nitrogen atmosphere after which MeOH and a saturated
solution of NH Cl were added and the reaction mixture stirred for a further 30 min. while
4
warming to room temperature. The mixture was partitioned between diethyl ether and water.
The organic layer was washed 3 times with water and the combined organic layers were dried
over MgSO and concentrated in vaccuo. The residue was dissolved in anhydrous THF (1mL),
4
and n-BuLi (1.5 equiv., 0.14 mL) was added, followed by tert-butylnitrite (8 equiv., 0.11 mL)
under nitrogen atmosphere. The reaction was stirred overnight. The mixture was partitioned
between diethyl ether and a saturated aqueous solution of K CO . The organic layer was
2
3
washed 3 times with saturated aqueous K CO , dried over MgSO , filtered and concentrated
2
3
4
in vaccuo to give a residue which was purified by flash column chromatography (SiO2,
Petrol:EtOAc 2%) to give the title compound 14d (27 mg, 53% over 2 steps) as a colourless
oil.
-1
1
R 0.26 (Petrol:EtOAc 8:2); IR ν (neat/cm ) 3444 (O-H); H NMR (400MHz, CDCl )
f
max
3
1
3
δ 7.49 (d, J = 7.3 Hz, 4H(aro)), 7.38-7.19 (m, 11H(aro)), 2.65 (s, 4H), 2.20 (s, 1H(-OH)), C
NMR (100MHz, CDCl ) δ 146.8, 142.3, 128.4, 128.3, 128.2, 126.9, 126.0, 125.8, 78.2, 44.0,
3
+
+
3
0.2; MS m/z (ES+) 311 (100%, M+Na ); HMRS (ES+) calcd for C H O Na (M+H ):
21 20 1 1
3
11.1404, found: 311.1405.
3
-Methyl-1,1-diphenylbutan-1-ol 14e. General procedure H was followed. 1-Phenylvinyl
isopropylphenylcarbamate 3b (45 mg) gave after flash column
c
c
b
chromatography (SiO , Petrol:EtOAc 1%) the title compound 14e (28
2
a
OH
mg, 73 %) as a colourless oil.
2
1

-1
1
R 0.53 (Petrol:EtOAc 8:2); IR ν (neat/cm ) 3472 (O-H); H NMR (500MHz, CDCl ) δ
f
max
3
7
1
1
.43 (d, J = 7.7 Hz, 4H(aro)), 7.32-7.20 (m, 6H(aro)), 2.25 (d, J = 5.7 Hz, 2H ), 2.04 (s, 1H(-OH)),
(a)
1
3
.76-1.66 (sept, J = 6.5 Hz, 1H ), 0.88 (d, J = 6.6 Hz, 6H ); C NMR (125MHz, CDCl ) δ
(b)
(c)
3
47.6, 128.0, 126.7, 126.0, 78.8, 50.3, 24.6, 24.3; EI GC/MS 183 (M-C H ).
4
9
3
-Methyl-1,1-diphenylpentan-1-ol 14h. General procedure H was followed. 1-Phenylvinyl
isopropylphenylcarbamate 3b (50 mg) gave after flash column
c
e
b
d
chromatography (SiO , Petrol:EtOAc 1%) the title compound 14h (29
2
OH
a
mg, 64 %) as a colourless oil.
1
R 0.29 (Petrol:EtOAc 9:1); H NMR (400MHz, CDCl ) δ 7.44 (d, J =
f
3
8
.0 Hz, 4H(aro)), 7.33-7.20 (m, 6H(aro)), 2.36 (dd, J = 14.3, 4.1 Hz, 1H(a)),
2
1
1
.15 (dd, J = 14.0, 6.8 Hz, 1H ), 2.03 (s, 1H ), 1.54-1.45 (m, 1H ), 1.38-1.28 (m, 1H ),
(a)
(-OH)
(b)
(c)
1
3
.22-1.12 (m, 1H ), 0.83-0.77 (m, 6H
); C NMR (100MHz, CDCl ) δ 147.8, 147.4,
3
(c)
(d)(e)
28.0, 126.7, 126.6, 126.1, 126.0, 78.7, 48.3, 31.2, 30.2, 21.2, 11.2; MS m/z (ES-) 253 (100%,
+
M-H ).
3
,3-Dimetyl-1,1-diphenylbutan-1-ol 14k. General procedure H was followed. 1-Phenylvinyl
isopropylphenylcarbamate 3b (50 mg) gave after flash column
b
b
b
chromatography (SiO , Petrol:EtOAc 1%) the title compound 14k (32
2
a
OH
mg, 71%) as a white solid.
1
R 0.29 (Petrol:EtOAc 9:1); m.p. 70-72°C; H NMR (400MHz, CDCl )
f
3
δ 7.49 (d, J = 7.2 Hz, 4H(aro)), 7.31-7.18 (m, 6H(aro)), 2.43 (s, 2H ), 2.05
(a)
1
3
(
s, 1H(-OH)), 0.86 (s, 9H ); C NMR (100MHz, CDCl ) δ 148.5, 127.9, 126.4, 125.8, 78.5,
(b) 3
+
5
3.0, 31.9, 31.7; MS m/z (ES-) 253 (100%, M-H ).
1
-(4-Chlorophenyl)-1-phenylhexan-1-ol 14b. General procedure H was followed. 1-
Phenylvinyl 4-chlorophenylisopropylcarbamate 3c and 1-(4-
e
d
chlorophenyl)vinyl isopropylphenylcarbamate 3d (50 mg) gave after
c
b
flash column chromatography (SiO , Petrol:EtOAc 1%) the title
2
a
OH
compounds 14b (35 mg, 77 %, 25 mg, 55 %) as a colourless oil.
-
1
1
R 0.65 (Petrol:EtOAc 8:2); IR ν
f
(neat/cm ) 3464 (O-H); H
max
Cl
NMR (400MHz, CDCl ) δ 7.40-7.21 (m, 9H(aro)), 2.24 (t, J = 7.6 Hz,
3
1
3
2
H ), 2.08 (s, 1H(-OH)), 1.30-1.18 (m, 6H(b)(c)(d)), 0.85 (t, J = 6.9 Hz, 3H(e)); C NMR
(a)
2
2

(
100MHz, CDCl ) δ 146.8, 145.7, 132.5, 128.2, 128.2, 127.5, 127.0, 125.9, 77.9, 41.8, 32.1,
3
+
+
2
2
3.3, 22.5, 14.0; MS m/z (ES-) 287 (100%, M-H ); HMRS (ES+) calcd for C H O Cl (M ):
18 21 1 1
88.1275, found: 288.1276; MS (EI) 217 (M-C H ).
4
9
1
-(4-Chlorophenyl)-3-methyl-1-phenylbutan-1-ol 14f. General procedure H was followed.
-Phenylvinyl 4-chlorophenylisopropylcarbamate 3c and 1-(4-
1
c
c
b
chlorophenyl)vinyl isopropylphenylcarbamate 3d (50 mg) gave after
a
OH
flash column chromatography (SiO , Petrol:EtOAc 1%) the title
2
compound 14f (28 mg, 65 % and 22 mg, 51 %) as a colourless oil.
Cl
-1
1
R 0.55 (Petrol:EtOAc 8:2); IR ν
f
(neat/cm ) 3464 (O-H);
H
max
NMR (400MHz, CDCl ) δ 7.42-7.22 (m, 9H ), 2.22 (d, J = 5.7 Hz, 2H ), 2.01 (s, 1H(-OH)),
3
(aro)
(a)
1
3
1
.69 (sept, J = 6.6 Hz, 1H ), 0.89 (d, J = 6.7 Hz, 3H ), 0.87 (d, J = 6.7 Hz, 3H ); C
(b) (c) (c’)
NMR (100MHz, CDCl ) δ 147.2, 146.0, 132.4, 128.2, 128.1, 127.5, 127.0, 125.9, 78.4, 50.2,
3
+
+
2
4.6, 24.5, 24.2; MS m/z (ES-) 273 (100%, M-H ); HMRS (ES+) calcd for C H O Cl (M ):
17 19 1 1
2
74.1107, found: 274.1119; MS (EI) 217 (M-C H ).
4
9
1
-(4-Chlorophenyl)-3-methyl-1-phenylpentan-1-ol 14i. General procedure H was followed.
1
-Phenylvinyl 4-chlorophenylisopropylcarbamate 3c and 1-(4-
c
e
b
d
chlorophenyl)vinyl isopropylphenylcarbamate 3d (50 mg) gave after
a
OH
flash column chromatography (SiO , Petrol:EtOAc 1%) the title
2
compound 14i (30 mg, 67 % and 23 mg, 51 %) as a yellow oil.
Cl
1
R 0.55 (Petrol:EtOAc 8:2); H NMR (500MHz, CDCl ) δ 7.42-7.22
f
3
(
9H(aro)), 2.33 (dd, J = 14.3, 4.0 Hz, 1H ), 2.12 (dd, J = 14.5, 7.0 Hz, 1H ), 2.00 (s, 1H, -
(a) (a’)
OH), 1.56-1.44 (m, 1H ), 1.39-1.27 (m, 1H ), 1.23-1.12 (m, 1H ), 0.85-0.78 (m, 6H(d)(e));
(b)
(c)
(c)
1
3
C NMR (125MHz, CDCl ) δ 147.5, 147.1, 146.3, 145.9, 132.5, 132.4, 128.2, 128.1, 127.6,
3
1
27.5, 127.0, 126.9, 126.0, 125.9, 78.5, 78.4, 48.2, 48.1, 31.2, 31.1, 30.3, 30.2, 21.1, 21.0,
+
+
1
1.1; MS m/z (ES-) 287 (100%, M-H ); HMRS (ES+) calcd for C H O Cl (M ): 288.1275,
18 21 1 1
found: 288.1276; MS (EI) 217 (M-C H ).
4
9
2
3

1
-(4-Chlorophenyl)-3,3-dimethyl-1-phenylbutan-1-ol 14l. General procedure H was
followed. 1-Phenylvinyl 4-chlorophenylisopropylcarbamate 3c and 1-
b
b
b
(4-chlorophenyl)vinyl isopropylphenylcarbamate 3d (50 mg) gave
a
OH
after flash column chromatography (SiO , Petrol:EtOAc 1%) the title
2
compound 14l (12 mg, 27 % and 16 mg, 36 %) as a yellow oil.
1
Cl
R 0.63 (Petrol:EtOAc 8:2); H NMR (500MHz, CDCl ) δ 7.46-7.42
f
3
1
3
(
m, 4H(aro)), 7.31-7.19 (m, 5H(aro)), 2.40 (s, 2H ), 2.03 (s, 1H(-OH)), 0.86 (s, 9H ); C NMR
(a) (b)
(
125MHz, CDCl ) δ 148.3, 146.9, 132.2, 128.1, 128.0, 127.3, 126.7, 125.6, 78.2, 53.0, 31.9,
3
+
3
1.7; MS m/z (ES-) 287 (60%, M-H ).
1
-(4-Methoxyphenyl)-1-phenylhexan-1-ol 14c. General procedure H was followed. 1-(4-
Methoxyphenyl)vinyl isopropylphenylcarbamate 3e (50 mg) gave
e
d
after flash column chromatography (SiO , Petrol:EtOAc 1%) the
2
c
b
title compound 14c (31 mg, 68 %) as a colourless oil.
a
OH
-1
1
R 0.46 (Petrol:EtOAc 8:2); IR ν (neat/cm ) 3492 (O-H);
H
f
max
NMR (500MHz, CDCl ) δ 7.39 (d, J = 5.9 Hz, 2H(aro)), 7.33-7.20
3
MeO
f
(
m, 5H(aro)), 6.84 (d, J = 7.1 Hz, 2H(aro)), 3.79 (s, 3H ), 2.24 (t, J =
(f)
1
3
6
.1 Hz, 2H ), 2.06 (s, 1H(-OH)), 1.29-1.24 (m, 6H(b)(c)(d)), 0.85 (t, J = 5.4 Hz, 3H ); C NMR
(a) (e)
(
125MHz, CDCl ) δ 158.3, 147.3, 139.5, 128.0, 127.3, 126.6, 125.9, 113.4, 78.0, 55.2, 42.0,
3
+
3
2.2, 23.5, 22.5, 14.0; MS m/z (ES-) 283 (100%, M-H ).
1
-(4-Methoxyphenyl)-3-methyl-1-phenylbutan-1-ol 14g. General procedure H was
followed. 1-(4-Methoxyphenyl)vinyl isopropylphenylcarbamate
c
c
b
3
e (50 mg) gave after flash column chromatography (SiO2,
a
OH
Petrol:EtOAc 1%) the title compound 14g (35 mg, 81 %) as a
colourless oil.
MeO
d
-1
1
R 0.39 (Petrol:EtOAc 8:2); IR ν (neat/cm ) 3473 (O-H); H
f
max
NMR (400MHz, CDCl ) δ 7.41 (d, J = 7.3 Hz, 2H(aro)), 7.34-7.19 (m, 7H(aro)), 6.83 (d, J = 8.8
3
Hz, 2H(aro)), 3.78 (s, 3H ), 2.21 (d, J = 5.7 Hz, 2H ), 2.00 (s, 1H(-OH)), 1.69 (sept, J = 6.3 Hz,
(d)
(a)
1
3
1
H ), 0.89 (d, J = 6.8 Hz, 3H ), 0.85 (d, J = 6.8 Hz, 3H ); C NMR (100MHz, CDCl )
(b) (c) (c) 3
δ 158.2, 147.7, 140.0, 128.0, 127.2, 126.5, 126.0, 113.3, 78.5, 55.2, 50.4, 24.6, 24.3; MS m/z
+
(
ES-) 269 (40%, M-H ), 255 (100%, M-CH ).
3
2
4

1
-(4-Methoxyphenyl)-3-methyl-1-phenylpentan-1-ol 14j. General procedure H was
followed. 1-(4-Methoxyphenyl)vinyl isopropylphenylcarbamate 3e
c
e
b
d
(50 mg) gave after flash column chromatography (SiO2,
a
OH
Petrol:EtOAc 1%) the title compound 14j (29 mg, 64%) as a
colourless oil.
MeO
f
1
R 0.44 (Petrol:EtOAc 8:2); H NMR (500MHz, CDCl ) δ 7.41 (d,
f
3
J = 7.3 Hz, 2H(aro)), 7.28-7.19 (m, 5H(aro)), 6.83 (d, J = 8.8 Hz, 2H(aro)), 3.79, 3.78 (2s, 3H(f)),
.32 (dd, J = 14.3, 4.0, 1H ), 2.11 (dd, J = 14.3, 6.7 Hz, 1H ), 1.98 (s, 1H(-OH)), 1.53-1.44
2
(a)
(a’)
1
3
(
m, 1H ), 1.38-1.21 (m, 1H ), 1.21-1.10 (m, 1H ), 0.84-0.75 (m, 6H(d)(e)); C NMR
(b) (c) (c’)
(
125MHz, CDCl ) δ 158.3, 158.2, 147.9, 147.6, 140.2, 139.8, 128.0, 127.3, 127.2, 126.6,
3
1
1
26.5, 126.0, 125.9, 113.3, 78.5, 78.4, 55.2, 48.4, 48.3, 31.2, 31.1, 30.3, 30.2, 21.1, 21.0, 11.2,
+
1.1; MS m/z (ES-) 283 (100%, M-H ).
1
-(4-Methoxyphenyl)-3,3-dimethyl-1-phenylbutan-1-ol 14m. General procedure H was
followed. 1-(4-Methoxyphenyl)vinyl isopropylphenylcarbamate 3e
b
b
b
(50 mg) gave after flash column chromatography (SiO2,
a
OH
Petrol:EtOAc 1%) the title compound 14m (30 mg, 67%) as a
yellow oil.
MeO
c
-1
1
R 0.33 (Petrol:EtOAc 8:2); IR ν (neat/cm ) 3494 (O-H);
H
f
max
NMR (400MHz, CDCl ) δ 7.45 (d, J = 7.2 Hz, 2H(aro)), 7.37 (d, J = 8.9 Hz, 2H(aro)), 7.28 (t, J
3
=
7.3 Hz, 2H(aro)), 7.18 (t, J = 7.3 Hz, 1H(aro)), 6.81 (d, J = 8.9 Hz, 2H(aro)), 3.77 (s, 3H ), 2.38
(c)
1
3
(
s, 2H ), 2.00 (s, 1H
), 0.85 (s, 9H ); C NMR (100MHz, CDCl ) δ 158.1, 148.6, 141.0,
(
a)
(-OH) (b) 3
1
27.9, 127.0, 126.3, 125.8, 113.2, 78.3, 55.1, 53.1, 31.9, 31.7;
1
,2-Diphenylhexyl isopropylphenylcarbamate 16g. General procedure I was followed. (Z)-
,2-Diphenylvinyl isopropylphenylcarbamate 3g (50 mg) gave
1
f
flash column chromatography (SiO , Petrol:EtOAc 1%) the title
2
e
d
b
compound 16g (40 mg, 70 %) as a white solid.
Ph
O
c
-1
R 0.50 (Petrol:EtOAc 8:2); m.p. 80-82°C; IR ν (neat/cm )
f
max
N
O a
1
1
3
688 (C=O); H NMR (400MHz, CDCl ) δ 7.41-7.38 (m,
3
g
h
h
H(aro)), 7.18-6.91 (m, 10H(aro)), 6.60 (br m, 2H(aro)), 5.81 (d, J =
6
.4 Hz, 1H ), 4.48 (sept, J = 6.8 Hz, 1H ), 2.70 (br s, 1H ), 1.53-1.41 (m, 2H ), 1.24-1.07
(a) g) (b) (c)
1
3
(
m, 2H(d)(e)), xx (d, J = 6.8 Hz, 3H ), xx (d, J = 6.8 Hz, 3H ), 0.74 (t, J = 7.2 Hz, 3H ); C
(h) (h’) (f)
2
5

NMR (100MHz, CDCl ) δ 154.4, 140.7, 140.3, 138.0, 130.3, 128.9, 128.6, 127.8, 127.5,
3
1
27.3, 127.2, 126.5, 125.9, 79.8, 52.0, 48.3, 31.7, 29.4, 22.5, 21.2, 13.8; MS m/z (ES+) 438
+
+
(
100%, M+Na ), (ES-) 414 (100%, M-H ).
The syn-stereochemistry was proved by an X-ray crystal structure:
1
,2-Diphenylhexyl 4-chlorophenylisopropylcarbamate 16h. General procedure I was
followed. (Z)-1,2-diphenylvinyl 4-
f
chlorophenylisopropylcarbamate 3h (50 mg) gave flash
e
d
b
column chromatography (SiO , Petrol:EtOAc 1%) the title
2
Cl
Ph
O
c
compound 16h (44 mg, 80 %) as a white solid.
N
O a
R 0.64 (Petrol:EtOAc 8:2); m.p. 93-95°C; IR ν
f
max
g
-1
1
h
h
(
neat/cm ) 1687 (C=O); H NMR (400MHz, CDCl ) δ 7.35
3
(d, J = 8.6 Hz, 2H(aro)), 7.23-7.09 (m, 6H(aro)), 6.98 (br m, 2H(aro)), 6.80 (d, J = 8.6 Hz, 2H(aro)),
6
1
3
1
.71 (br m, 2H(aro)), 5.82 (d, J = 7.2 Hz, 1H ), 4.46 (sept, J = 6.8 Hz, 1H ), 2.73 (br s, 1H ),
(a) g) (b)
.55-1.38 (m, 2H ), 1.21-0.96 (m, 2H
), 0.99 (d, J = 6.8 Hz, 3H ), 0.93 (d, J = 6.8 Hz,
(h)
(c)
(d)(e)
1
3
H ), 0.74 (t, J = 7.2 Hz, 3H ); C NMR (100MHz, CDCl ) δ 154.2, 140.8, 140.2, &36.5,
(h’)
(f)
3
31.5, 128.8, 127.4, 126.6, 126.1, 114.2, 80.1, 52.0, 48.3, 31.8, 29.3, 22.4, 21.1, 13.8 ; MS
+
+
m/z (ES+) 472 (100%, M+Na ); HMRS (ES+) calcd for C H O N Cl (M+H ): 450.2194,
2
8
33
2
1
1
found: 450.2205.
1
,1,2-Triphenylhexan-1-ol 18g. General procedure J was followed. (Z)-1,2-diphenylvinyl 4-
chlorophenylisopropylcarbamate 3g (50 mg) gave after flash column
e
d
chromatography (SiO , Petrol:EtOAc 1%) the title compound 18g (28 mg,
2
c
b
a
6
0 %) as a white solid.
OH
1
Ph
R 0.61 (Petrol:EtOAc 8:2); m.p. 99-101°C; H NMR (400MHz, CDCl )
f
3
δ 8.61-8.00 (m, 15H(aro)), 4.71 (dd, J = 11.6, 2.8 Hz, 1H ), 3.45 (s, 1H, -
(a)
2
6

1
3
OH), 2.91-2.72 (m, 2H H ), 2.35-2.03 (m, 4H H
), 1.78 (t, J = 7.2 Hz, 3H ); C NMR
(e)
,
(b)
,
(c)(d)
(
400MHz, CDCl ) δ 146.4, 146.0, 140.0, 130.0, 128.2, 127.7, 127.5, 126.7, 126.3, 126.2,
3
+
1
26.1, 125.6, 80.9, 54.1, 30.2, 29.8, 22.6, 13.9; MS m/z (ES+) 353 (100%, M+Na ); HMRS
+
(
ES+) calcd for C H O (M+Na ): found: 353.1876.
2
4
26
1
1
-(4-Chlorophenyl)-1,2-diphenylhexan-1-ol 18h. General procedure J was followed. (Z)-
,2-diphenylvinyl 4-chlorophenylisopropylcarbamate 3h (50 mg) gave
1
e
d
after flash column chromatography (SiO , Petrol:EtOAc 1%) the title
2
c
b
a
compound 18h (25 mg, 54 %) as a colourless oil.
OH
Ph
1
R 0.34 (Petrol:EtOAc 8:2); H NMR (400MHz, CDCl ) δ 7.50-6.93
f
3
(
m, 14H(aro)), 3.59, 3.58 (2t, J = 12.0 Hz, 1H ), 2.37, 2.35 (2s, 1H(-OH)),
(a)
Cl
1.80-1.56 (m, 2H ), 1.24-0.94 (m, 4H(c)(d)), 0.68 (t, J = 7.0 Hz, 3H(e));
(b)
1
3
C NMR (100MHz, CDCl ) δ 145.9, 145.8, 145.0, 144.5, 139.8, 139.6, 130.0, 129.9, 128.4,
3
1
5
28.2, 127.8, 127.7, 127.6, 127.1, 126.9, 126.5, 126.4, 126.3, 126.1, 125.6, 80.7, 80.6, 54.0,
+
4.0, 30.1, 29.8, 29.7, 22.6, 13.9 ; MS m/z (ES-) 363 (100%, M+H ).
2
,2-Dimethyl-5-phenyldec-3-yn-5-ol 21a. General procedure H was followed. 5,5-
Dimethylhex-1-en-3-yn-2-yl isopropylphenylcarbamate 8a (50 mg)
e
d
gave after flash column chromatography (SiO , Petrol:EtOAc 1%) the
2
c
b
title compound 21a (32 mg, 71 %) as a colourless oil.
HO
a
-1
1
R 0.55 (Petrol:EtOAc 8:2); IR ν (neat/cm ) 3224 (O-H); H-NMR
f
max
f
f
(
400MHz, CDCl ) δ 7.62 (d, J = 7.3 Hz, 2H(aro)), 7.37-7.25 (m, 3H(aro)),
3
2
.29 (s, 1H(-OH)), 1.94-1.76 (m, 2H ), 1.52-1.40 (m, 1H ), 1.34-1.22
(a) (b)
f
1
3
(
m, 5H(b’)(c)(d)), 1.29 (s, 9H ), 0.86 (t, J = 6.6 Hz, 3H ); C-NMR (100MHz, CDCl ) δ 145.5,
(f) (e) 3
1
2
2
27.9, 127.3, 125.5, 95.1, 81.0, 73.3, 45.6, 31.6, 31.0, 27.5, 24.4, 22.4, 13.9 ; MS m/z (ES+)
+
+
81 (100%, M+Na ); HMRS (ES+) calcd for C H O Na (M+Na ): 281.1876, found:
1
8
26
1
1
81.1866.
2
,7,7-Trimethyl-4-phenyloct-5-yn-4-ol 21b. General procedure H was followed. 5,5-
Dimethylhex-1-en-3-yn-2-yl isopropylphenylcarbamate 8a (50 mg)
c
c
b
gave after flash column chromatography (SiO , Petrol:EtOAc 1%)
2
HO
a
the title compound 21b (31 mg, 74 %) as a colourless oil.
d
d
d
2
7

-1
1
R 0.55 (Petrol:EtOAc 8:2); IR ν
f
(neat/cm ) 3436 (O-H); H-NMR (400MHz, CDCl )
3
max
δ 7.64 (d, J = 7.0 Hz, 2H(aro)), 7.37-7.26 (m, 3H(aro)), 2.26 (s, 1H(-OH)), 1.88-1.75 (m, 3H(a)(b)),
1
3
1
.30 (s, 9H ), 0.98 (d, J = 6.4 Hz, 3H ), 0.84 (d, J = 6.4 Hz, 3H ) ; C-NMR (100MHz,
(d) (c) (c)
CDCl ) δ 145.9, 128.0, 127.3, 125.5, 95.1, 81.4, 73.0, 53.9, 30.9, 27.5, 25.1, 24.1, 23.9 ; MS
3
+
+
m/z (ES+) 267 (100%, M+Na ); HMRS (ES+) calcd for C H O Na (M+Na ): 267.1719,
1
7
24
1
1
found: 267.1727.
2
,2,7,7-Tetramethyl-4-phenyloct-5-yn-4-ol 21c. General procedure H was followed. 5,5-
Dimethylhex-1-en-3-yn-2-yl isopropylphenylcarbamate 8a (50 mg)
b
b
b
gave after flash column chromatography (SiO , Petrol:EtOAc 1%) the
2
title compound 21c (30 mg, 67 %) as a colourless oil.
HO
a
-1
1
R 0.67 (Petrol:EtOAc 8:2); IR ν
f
(neat/cm ) 3443 (O-H); H-
max
c
c
NMR (400MHz, CDCl ) δ 7.66 (d, J = 7.2 Hz, 2H(aro)), 7.36-7.25 (m,
3
c
3
H(aro)), 2.21 (s, 1H(-OH)), 1.94 (d, J = 14.4 Hz, 1H ), 1.83 (d, J =
(a)
1
3
1
1
4.4 Hz, 1H ), 1.28 (9H ), 0.98 (s, 9H ) ; C-NMR (100MHz, CDCl ) δ 147.2, 127.9,
(a’) (c) (b) 3
27.2, 125.6, 95.6, 82.1, 72.5, 57.2, 31.4, 30.9, 30.7, 27.5 ; MS m/z (ES+) 281 (100%,
+
+
M+Na ); HMRS (ES+) calcd for C H O Na (M+Na ): 281.1876, found: 281.1877.
1
8
26
1
1
5
-(4-Chlorophenyl)-2,2-dimethyldec-3-yn-5-ol 21d. General procedure H was followed.
,5-Dimethylhex-1-en-3-yn-2-yl 4-
5
e
d
chlorophenylisopropylcarbamate 8b (50 mg) gave after flash
c
b
column chromatography (SiO , Petrol:EtOAc 1%) the title
2
HO
a
compound 21d (20 mg, 40 %) as a colourless oil.
f
f
-
1
1
R 0.57 (Petrol:EtOAc 8:2); IR ν (neat/cm ) 3393 (O-H); H-
f
max
Cl
NMR (400MHz, CDCl ) δ 7.53 (dd, J = 8.8, 2.8 Hz, 2H(aro)), 7.30
3
f
(d, J = 8.8 Hz, 2H(aro)), 2.27 (s, 1H(-OH)), 1.90-1.72 (m, 2H(a)),
1
3
1
.48-1.21 (m, 6H(b)(c)(d)), 1.27 (s, 9H ), 0.85 (t, J = 6.8 Hz, 3H ); C-NMR (100MHz,
(f) (e)
CDCl ) δ 144.1, 133.1, 128.0, 127.0, 95.4, 80.7, 72.8, 45.6, 31.6, 30.9, 27.4, 24.3, 22.4, 13.9 ;
3
+
MS m/z (ES+) 275 (100%, M-H O+H ); HMRS (ES+) found: 275.1561.
2
2
8

4
-(4-Chlorophenyl)-2,7,7-trimethyloct-5-yn-4-ol 21e. General procedure H was followed.
5
,5-Dimethylhex-1-en-3-yn-2-yl
4-
c
c
b
chlorophenylisopropylcarbamate 8b (50 mg) gave after flash
HO
a
column chromatography (SiO , Petrol:EtOAc 1%) the title
2
d
d
compound 21e (12 mg, 43 %) as a colourless oil.
Cl
-1
d
R 0.64 (Petrol:EtOAc 8:2); IR ν (neat/cm ) 3409 (O-H), 2240
f
max
1
(
C≡C); H-NMR (400MHz, CDCl ) δ 7.55 (d, J = 8.7 Hz, 2H(aro)), 7.30 (d, J = 8.7 Hz, 2H(aro)),
3
2
6
5
.20 (s, 1H(-OH)), 1.82-1.70 (m, 3H(a)(b)), 1.27 (s, 9H ), 0.96 (d, J = 6.4 Hz, 3H ), 0.83 (d, J =
(d) (c)
1
3
.4 Hz, 3H ) ; C-NMR (400MHz, CDCl ) δ 144.5, 133.1, 128.1, 127.0, 95.5, 81.0, 72.6,
(c’)
3
+
3.9, 30.8, 27.5, 25.1, 24.1, 23.9 ; MS m/z (ES+) 261 (100%, M-H O+H ); HMRS (ES+)
2
found: 261.1405.
4
-(4-Chlorophenyl)-2,2,7,7-tetramethyloct-5-yn-4-ol 21f. General procedure H was
followed. 5,5-Dimethylhex-1-en-3-yn-2-yl 4-
b
b
b
chlorophenylisopropylcarbamate 8b (50 mg) gave after flash
HO
a
column chromatography (SiO , Petrol:EtOAc 1%) the title
2
c
c
compound 21f (21 mg, 47 %) as a colourless oil.
-1
1
Cl
R 0.55 (Petrol:EtOAc 8:2); IR ν (neat/cm ) 3434 (O-H); H-
f
max
c
NMR (400MHz, CDCl ) δ 7.56 (d, J = 8.8 Hz, 2H(aro)), 7.29 (d, J
3
=
8.8 Hz, 2H(aro)), 2.21 (s, 1H(-OH)), 1.89 (d, J = 14.4 Hz, 1H ), 1.78 (d, J = 14.4 Hz, 1H ),
(a) (a’)
1
3
1
.26 (s, 9H ), 0.97 (s, 9H ) ; C-NMR (100MHz, CDCl ) δ 145.8, 133.0, 128.0, 127.1,
(c) (b) 3
+
9
5.9, 81.7, 72.1, 57.2, 31.4, 31.0, 30.6, 27.5 ; MS m/z (ES+) 275 (100%, M-H O+H ); HMRS
2
+
(
ES+) calcd for C H O Cl (M-H O+H ): 275.1561, found: 275.1550.
1
8
24
1
1
2
2
,2-Dimethyl-5-p-tolyldec-3-yn-5-ol 21g. General procedure H was followed. 5,5-Dimethyl-
-en-3-yn-2-yl isopropyl-p-tolylcarbamate 8c (50 mg) gave after
1
e
d
flash column chromatography (SiO , Petrol:EtOAc 1%) the title
2
c
b
compound 21g (17 mg, 34 %) as a colourless oil.
HO
a
-1
R 0.65 (Petrol:EtOAc 8:2); IR ν (neat/cm ) 3426 (O-H), 2242
f
max
f
1
(
C≡C); H-NMR (400MHz, CDCl ) δ 7.50 (d, J = 8.0 Hz, 2H(aro)),
3
g
f
f
7.15 (d, J = 8.0 Hz, 2H(aro)), 2.35 (s, 3H ), 2.22 (s, 1H(-OH)), 1.92-
(g)
1
3
1
.74 (m, 2H ), 1.51-1.26 (m, 6H
), 1.28 (s, 9H ), 0.85 (t, J = 6.8 Hz, 3H ); C-NMR
(a)
(b)(c)(d) (f) (e)
(
100MHz, CDCl ) δ 142.7, 137.0, 128.6, 125.4, 94.9, 81.1, 73.2, 45.5, 31.6, 31.0, 27.4, 24.4,
3
2
9

+
+
2
2.4, 21.0, 13.9 ; MS m/z (ES+) 255 (90%, M-H O+H ), 295 (60%, M+Na ); HMRS (ES+)
2
+
calcd for C H O (M-H O+H ): 255.2108, found: 255.2151.
1
9
27
1
2
2
,7,7-Trimethyl-4-p-tolyloct-5-yn-4-ol 21h. General procedure H was followed. 5,5-
Dimethyl-1-en-3-yn-2-yl isopropyl-p-tolylcarbamate 8c (50 mg)
c
c
b
gave after flash column chromatography (SiO , Petrol:EtOAc 1%)
2
HO
a
the title compound 21h (18 mg, 44 %) as a colourless oil.
d
d
-1
R 0.68 (Petrol:EtOAc 8:2); IR ν (neat/cm ) 3429 (O-H), 2239
f
max
e
1
(
C≡C); H-NMR (400MHz, CDCl ) δ 7.51 (d, J = 8.2 Hz, 2H(aro)),
3
d
7
.15 (d, J = 8.2 Hz, 2H(aro)), 2.34 (s, 3H ), 2.17 (s, 1H(-OH)), 1.85-
(e)
1
3
1
.73 (m, 3H(a)(b)), 1.27 (s, 9H ), 0.97 (d, J = 6.3 Hz, 3H ), 0.83 (d, J = 6.3 Hz, 3H ) ; C-
(d) (c) (c’)
NMR (100MHz, CDCl ) δ 143.1, 137.0, 128.6, 125.4, 95.0, 81.5, 72.9, 53.8, 30.9, 27.4, 24.1,
3
+
+
2
1.0 ; MS m/z (ES+) 281 (100%, M+Na ), 241 (70%, M-H O+H ); HMRS (ES+) calcd for
2
+
C H O (M-H O+H ): 241.1951, found: 241.1962.
18
25
1
2
4
-(3-(Trifluoromethyl)phenyl)-2,7,7-trimethyloct-5-yn-4-ol 21i. General procedure H was
followed.
5,5-Dimethyl-1-en-3-yn-2-yl
3-
c
c
b
(
trifluoromethyl)phenylisopropylcarbamate 8d (50 mg) gave
HO
a
F3C
after flash column chromatography (SiO , Petrol:EtOAc 1%) the
2
d
d
title compound 21i (24 mg, 55 %) as a orange oil.
-1
d
R 0.66 (Petrol:EtOAc 8:2); IR ν
(neat/cm ) 3307 (O-H),
f
max
1
2
240 (C≡C); H-NMR (400MHz, CDCl ) δ 7.92 (s, 1H(aro)), 7.80 (d, J = 7.8 Hz, 1H(aro)), 7.53
3
(d, J = 7.8 Hz, 1H(aro)), 7.45 (t, J = 7.8 Hz, 1H(aro)), 2.28 (s, 1H(-OH)), 1.84-1.71 (m, 3H(a)(b)),
1
3
1
.28 (s, 9H ), 0.98 (d, J = 6.3 Hz, 3H ), 0.86 (d, J = 6.3 Hz, 3H ) ; C-NMR (100MHz,
(d) (c) (c)
2
1
CDCl ) δ 147.2, 130.3 (q, J = 32 Hz, J ), 129.0, 128.5, 124.2 (q, J = 270 Hz, J ), 124.2
3
C-F
C-F
3
3
(
q, J = 3.7 Hz, J ), 122.5 (q, J = 3.7 Hz, J ), 95.9, 80.8, 72.8, 53.9, 30.8, 27.5, 25.2, 24.1,
C-F C-F
+
2
3.9 ; MS m/z (ES+) 295 (100%, M-H O+H ); HMRS (ES+) found: 295.1668.
2
4
-(3-(Trifluoroethyl)phenyl)-2,2,7,7-tetramethyloct-5-yn-4-ol 21j. General procedure H
was
followed.
5,5-Dimethyl-1-en-3-yn-2-yl
3-
b
b
b
(trifluoromethyl)phenylisopropylcarbamate 8d (50 mg) gave
HO
after flash column chromatography (SiO , Petrol:EtOAc 1%)
2
a
F3C
the title compound 21j (12 mg, 26 %) as a yellow oil.
c
c
c
3
0