Silver-catalyzed ring-opening of cyclopropenes: Preparation of tertiary α-branched allylic amines

Article abstract of DOI:10.1016/j.tet.2013.04.133

Herein we report a silver-catalyzed ring-opening of cyclopropenes by addition of amines. This transformation is thought to occur via an argentocarbenium intermediate and affords tertiary α-branched allylic amines in good yields and high regioselectivity. The protocol applies to various primary and secondary amines, as well as sterically hindered cyclopropenes. Friedel-Crafts cyclization of the cationic intermediate occurs as a competitive pathway to form methyl-indene.

Full text of DOI:10.1016/j.tet.2013.04.133

Accepted Manuscript
Silver-Catalyzed Ring-Opening of Cyclopropenes: Preparation of Tertiary α-Branched
Allylic Amines
Diem T.H. Phan, Vy M. Dong
PII:
S0040-4020(13)00707-2
10.1016/j.tet.2013.04.133
TET 24333
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 19 February 2013
Revised Date: 26 April 2013
Accepted Date: 29 April 2013
Please cite this article as: Phan DTH, Dong VM, Silver-Catalyzed Ring-Opening of Cyclopropenes:
Preparation of Tertiary α-Branched Allylic Amines, Tetrahedron (2013), doi: 10.1016/j.tet.2013.04.133.
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Silver-Catalyzed Ring-Opening of
Cyclopropenes: Preparation of 3° α-
Branched Allylic Amines
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Diem T. H. Phan, Vy M. Dong*
Department of Chemistry, University of California at Irvine, Irvine, CA, 92697-2025, USA

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1
Tetrahedron
journal homepage: www.elsevier.com
Silver-Catalyzed Ring-Opening of Cyclopropenes: Preparation of Tertiary α-
Branched Allylic Amines
Diem T. H Phan , Vy M. Dong
Department of Chemistry, University of California at Irvine, Irvine, CA, 92697-2025, USA
Department of Chemistry, University of Toronto, Toronto, Ontario, M5S 3H6, Canada
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
Herein we report a silver-catalyzed ring-opening of cyclopropenes by addition of amines. This
transformation is thought to occur via an argentocarbenium intermediate and affords tertiary α-
branched allylic amines in good yields and high regioselectivity. The protocol applies to various
primary and secondary amines, as well as sterically hindered cyclopropenes. Friedel-Crafts
cyclization of the cationic intermediate occurs as a competitive pathway to form methyl-indene.
Available online
2009 Elsevier Ltd. All rights reserved.
Keywords:
hydroamination
cyclopropenes
ring-opening
silver catalysis
branched allylic amines
———
Corresponding author. Tel.: +1-949-824-9758; fax: +0-000-000-0000; e-mail: dongv@uci.edu

ACCEPTED MANUSCRIPT
2
Tetrahedron
1. Introduction
intermolecular hydroamination of alkenes has been previously
reported,7 however, no reactivity was observed with our
substrates (entry 2). Neutral Au(III) and Au(I) were ineffective
catalysts (entries 3-4),8 whereas a combination of PPh3AuCl and
AgNTf2 , afforded amine 3a along with a complex mixture of
unidentified by-products (entry 5). The active catalyst in this
reaction was assumed to be PPh3AuNTf2 which was formed in
situ. It should be noted that this catalyst was shown by Lee3d,f to
be the best catalyst for their regioselective addition of alcohols to
cyclopropenes.9 AgOTf showed superior activity compared to
other catalysts (entry 6a). We were encouraged by the high
regioselectivity (the linear product 3a’ was not observed). An
indene by-product 4a, however, was also observed. Attempts to
replace benzylamine with less nucleophilic aniline and amide
derivatives were met with poor reactivity. AgOTf proved to be
the most efficient catalyst among several silver salts evaluated,10
however, 20 mol% catalyst loading was required to achieve high
yields (Table 1, entry 6b, Table 2, entry 1).
Due to the large ring strain (ca. 228 kJ/mol) and enhanced π-
density of its double bond,1 cyclopropenes are more reactive than
simple olefins and thus attractive substrates for coordination
chemistry with π-philic transition metals.2 Transition metal
complexes can promote or catalyze the isomerisation of
cyclopropenes under mild conditions. Cyclopropenes are expected to
undergo ring-opening to produce an organometallic species that can
be viewed as
Table 1. Evaluation of Different Catalystsa
Scheme 1. Ring-Opening Reactions of Cyclopropenes
a hybrid between a metal-stabilized allylic carbocation and a metal
alkenyl carbene (Scheme 1a). This organometal carbenoid can
undergo self- or cross-carbene couplings and cyclopropanation of
olefins by acting as a diazoalkane equivalent. Alternatively this
intermediate can be intercepted in nucleophilic additions with arenes,
carbonyl groups, or alcohols.3 In the later context, Padwa3j first
reported an intermolecular trapping of the vinyl organosilver
intermediate4 with methanol to generate the branched allylic ether Ia
and branched allylic ether Ia and enone Ib products. The enone was
thought to result from oxidation of the corresponding linear allylic
ether (Scheme 1b).
entry
catalyst
Time 3a:3a’:4a’ (% yield)b
1a
2
None
HOTf
1d
1d
No reaction
No reaction
No reaction
<5 : 0 : trace
3
AuCl3
1d
4
AuClPPh3
AuClPPh3/AgNTf2
1d
5
2.5d
1:1 of 2a:3a, and by-
products
6a
AgOTf (10 mol%)
1.5d
70 : 0 : 11
6b
AgOTf (20 mol%)
1d
88 : 0 : 8
a Conditions: 0.2 mmol 1, 0.1 mmol 2a, 0.1 mL toluene.
b Based on 1H NMR integration of crude reaction mixtures.
With this protocol, we coupled various amine nucleophiles to
model cyclopropene 1 (Table 2). Having a substituent at the
ortho position of the benzyl ring causes a slight decrease in
reactivity (74% yield, entry 2). Electron-rich benzylamines 2c
and 2d were tolerated in good yields (entries 3, 4). The presence
of an electron-withdrawing substituent on the benzyl ring of 2e
diminished the yield slightly (67% yield, entry 5). Likewise,
extending the alkyl chain of the amine by one methylene unit (2f)
had a moderate influence on the reaction yield (67%, entry 6).
Even sterically encumbered secondary amine 2g was found to
cleanly react to give 3g in high yield (88%, entry 7). We
attribute this high reactivity to the enhanced nucleophilicity of
the cyclic structure. Lastly, racemic amine 2h with a methyl
substituent at the benzylic position afforded the product as a 1:1
mixture of diastereomers in 81% yield, athough a longer reaction
time was required (entry 8). No linear amine products were
observed in any of the reactions studied. The indene by-products
Scheme 2. Proposed ring-opening of cyclopropenes followed by
nucleophilic addition
Reported thirty years ago, Padwa's discovery was recently
expanded upon by Lee3d,f who used a cationic Au catalyst to
synthesize tertiary allylic ethers with high regioselectivity. We
wondered whether this catalytic strategy for making C–O bonds
could be applied for making C–N bonds,5 thus enabling an analogous
route to tertiary allylic amines. A Pd-catalyzed ring-opening/
hydroamination of cyclopropenes has been reported,6 and linear
allylic amines were obtained in this system. On the basis of these
reports, it occurred to us that a metal-stabilized allylic carbocation
could be intercepted by an amine to afford tertiary allylic amine
products
C after protodemetallation (Scheme 2). When the
cyclopropene bears an aryl substituent, indene E could form via a
Friedel-Crafts-type pathway. Herein, we report the first example of
ring-opening hydroamination of cyclopropenes to afford branch
selectivity.
1
were observed in 0 to 10% yields, as determined by H NMR
analysis of the crude reaction mixtures.
2. Results and discussion
Our initial study focused on the hydroamination of model
cyclopropene 1 with benzylamine 2a (Table 1). In the absence of
any catalyst, none of the possible products were observed and
starting materials were recovered (entry 1). The use of HOTf in

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Table 2. Hydroamination of 3,3-MethylPhenylCyclopropene 1a
Table 3. Hydroamination with Various Cyclopropenesa
Entry Amine
Product
% yield
a Conditions: 0.4mmol 1, 0.2mmol 2, 0.1mL toluene.
b 2 days
a
Conditions: 0.4 mmol cyclopropene, 0.2 mmol 2, 0.1 mL toluene, (%
isolated yield).
b 30 hours
The reaction scope was further evaluated by subjecting a
variety of cyclopropenes and amines to the optimized conditions
(Table 4). Cyclopropene 4 bearing an electron-donating OPh
group at the para-position reacted smoothly with different
amines to produce tertiary allylic amines in good yields (4a-c).
An alkylamine bearing a heteroaryl ring also proceeded well to
furnish product 4i in 73% yield. Changing the para substituent
from the OPh group to an electron-withdrawing Br group had no
detrimental influence on reactivity (5d, 5g and 5j). Notably,
cyclic aliphatic amine (i.e. 4-methylpiperidine) delivered product
5j in good yield (88%). Cyclopropene 6 with a more sterically
demanding 2-naphthyl group also afforded the corresponding
product (6g-73% yield, 6j-83% yield). Remarkably, when
combining the sterically hindered spiro-cyclopropene 7 with a
hindered secondary amine 2g, product 7g was produced in 89%
yield. We varied the phenyl substituent on the cyclopropene to a
heteroaromatic thienyl group and observed desired product in
good yield (8b, 75%). Lastly, we demonstrated that cyclic alkyl-
Given our proposed mechanism, which involves a cationic
intermediate, we were curious to see if asymmetric induction via
ion pairing with a chiral anionic counterion was feasible.11
A
preliminary study with chiral silver phosphate salts prepared
from commercially available chiral phosphoric acids, showed
promising reactivity with chiral silver salt AgP*, albeit with low
enantioselectivity (73 yield, 9% ee) (Scheme 3).
Scheme 3. Evaluation of Chiral Silver Salt
3. Conclusion
alkyl substituted cyclopropene
9 yielded a mixture of
diastereomers (9a, 69% combined yields, 2.8:1 dr).
In summary, we have disclosed a Ag-catalyzed ring-opening
addition of amines to 3,3-disubstituted cyclopropenes with high
regioselectivity. Several tertiary α-branched allylic amines were
prepared in good yields using an inexpensive Ag-catalyst. The
method encompasses several primary and secondary amines as

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4
Tetrahedron
NMR (100 MHz, CDCl3): δ 146.7, 145.2, 139.3, 136.8, 130.3,
nucleophiles. Our approach complements a small, but growing
128.8, 128.3, 127.0, 126.8, 126.7, 126.1, 113.2, 60.9, 45.1, 26.0,
19.2. IR (neat): 3059.7, 3021.9, 2924.7, 2973.6, 1634.1, 1600.7,
1490.0, 1445.6, 1367.2 cm-1. HR MS (ESI+): calculated for
[C18H22N]+ 252.1752, found 252.1757.
class of catalytic strategies for the construction of chiral tertiary
α-branched allylic amines.
4. Experimental section
4.1 General Considerations
N-(3-methoxybenzyl)-2-phenylbut-3-en-2-amine (3c): yellow
oil, 74% yield. H NMR (300 MHz, CDCl3): δ 7.55-7.52 (m,
1
Commercial reagents were purchased from Sigma Aldrich,
Strem, Alfa Aesar, and Acros and used without further
purification. All reactions were carried out under an argon
atmosphere, unless otherwise indicated. Toluene used in the
silver-catalyzed hydroamination reaction was dried through two
columns of activated alumina and then distilled over CaH2.
Reactions were monitored using thin-layer chromatography
(TLC) on EMD Silica Gel 60 F254 plates. Visualization of the
developed plates was performed under UV light (254 nm) or
KMnO4 stain. Column chromatography was performed with
Silicycle Silia-P Flash Silica Gel, using either glass columns or a
Biotage SP-1 system. Organic solutions were concentrated under
2H), 7.40-7.31 (m, 3H), 7.25-7.19 (m, 2H), 6.95 (s, 1H), 6.79-
6.76 (m, 1H), 6.09 (dd, J = 10.7 Hz, J = 17.5 Hz, 1H), 5.25 (dd,
J = 1.1 Hz, J = 10.6 Hz, 1H), 5.21 (dd, J = 1.1 Hz, J = 3.7 Hz,
1H), 3.80 (s, 3H), 3.59 (s, 2H), 1.57 (s, 3H), 1.55 (bs, 1H). 13C
NMR (75 MHz, CDCl3): δ 159.9, 146.5, 145.1, 143.2, 129.5,
128.4, 126.8, 126.7, 125.9, 120.6, 113.9, 113.2, 112.3, 60.9,
55.4, 47.4, 26.3. IR (neat): 3056.7, 2970.8, 2834.3, 1599.6,
1585.3, 1489.0, 1445.7, 1263.2 cm-1. HR MS (ESI+): calculated
for [C18H22NO]+ 268.1701, found 268.1695.
N-(benzo[d][1,3]dioxo-5-ylmethyl)-2-phenylbut-3-en-2-amine
(3d): yellow oil, 71% yield. 1H NMR (400 MHz, CDCl3): δ
7.54-7.53 (m, 1H), 7.51 (d, J = 1.1 Hz, 1H), 7.34 (t, J = 7.6 Hz,
2H), 7.25-7.21 (m, 1H), 6.89 (d, J = 1.4 Hz, 2H), 6.76 (dd, J =
16.6 Hz, J = 4.7 Hz, 1H), 6.08 (dd, J = 10.6 Hz, J = 17.6 Hz,
1H), 5.92 (s, 2H), 5.24 (dd, J = 1.2 Hz, J = 9.6 Hz, 1H), 5.20
(dd, J = 1.1 Hz, J = 2.8 Hz, 1H), 3.50 (d, J = 2.3 Hz, 2H), 1.56
(s, 3H), 1.53 (bs, 1H). 13C NMR (100 MHz, CDCl3): δ 147.5,
146.3, 146.2, 144.8, 135.3, 128.1, 126.5, 126.5, 120.9, 112.9,
108.7, 108.0, 100.8, 60.6, 47.0, 26.1. IR (neat): 2976.3, 2883.7,
1713.5, 1689.0, 1602.2, 1502.2, 1488.4, 1441.6, 1362.9, 1248.2
cm-1. HR MS (ESI+): calculated for [C18H20NO2]+ 282.1494,
found 282.1486.
1
reduced pressure on a Büchi rotary evaporator. H and 13C NMR
spectra were recorded on a Varian Mercury 300, Varian Mercury
400, Bruker 400 or a VRX-S (Unity) 400 spectrometer. NMR
spectra were internally referenced to the residual solvent signal
(TMS). Data for 1H NMR are reported as follows: chemical shift
(δ ppm), multiplicity (s = singlet, d = doublet, t = triplet, q =
quartet, m = multiplet, br = broad), coupling constant J (Hz),
integration. Data for 13C NMR are reported in chemical shift (δ
ppm). High resolution mass spectra (HRMS) were obtained on a
micromass 70S-250 spectrometer (EI) or an ABI/Sciex Qstar
Mass Spectrometer (ESI). Infrared (IR) spectra were obtained on
a Perkin-Elmer Spectrum 1000 FT-IR Systems and are reported
in terms of frequency of absorption (cm-1). Melting point ranges
were determined on a Fisher-Johns Melting Point Apparatus.
N-(3-chlorobenzyl-2-phenylbut-3-en-2-amine (3e): yellow oil,
1
67% yield. H NMR (300 MHz, CDCl3): δ 7.54-7.51 (m, 2H),
7.38-7.32 (m, 3H), 7.26-7.19 (m, 4H), 6.08 (dd, J = 10.8 Hz, J =
17.4 Hz, 1H), 5.26 (dd, J = 0.9 Hz, J = 7.6 Hz, 1H), 5.21 (s,
1H), 3.58 (s, 2H), 1.56 (s, 4H, overlapping CH3 and N-H peaks).
4.2 AgOTf-catalyzed hydroamination of cyclopropenes
General Procedure: In a flame-dried 1 dram vial containing a
stir bar, silver triflate (10.3 mg, 0.4 mmol, 20mol %) was
dissolved in 0.1 ml of anhydrous toluene. Amine (0.2 mmol) was
then added to the reaction vial via a micropipette, followed by
cyclopropene (0.4 mmol, 2 molar equivalents). The reaction vial
was then capped and stirred at 70 °C for 1 day (unless indicated
otherwise). The reaction mixture was then cooled down to room
temperature and the silver catalyst was removed by passing the
reaction mixture through a silica gel pipette plug using 10mL of
EtOAc as the eluent. The resulting organic solvents were
concentrated in vacuo. The allylic amine product 3 was isolated
by preparative thin layer chromatography. The allylic
amine:indene ratios were determined by 1H NMR analysis of the
crude reaction mixtures.
13C NMR (75 MHz, CDCl3):
δ 146.2, 144.9, 143.7, 134.3,
129.7, 128.4, 128.3, 127.1, 126.9, 126.7, 126.4, 113.3, 60.9, 47.0,
26.3. IR (neat): 3059.4, 2970.9, 2928.2, 2847.9, 1635.9, 1598.0,
1574.7, 1490.3, 1445.4, 1410.1 cm-1. HR MS (ESI+): calculated
for [C17H19ClN]+ 272.1206, found 272.1201.
N-phenethyl-2-phenylbut-3-en-2-amine (3f): yellow oil, 67%
1
yield. H NMR (300 MHz, CDCl3): δ 7.37-7.34 (m, 2H), 7.31-
7.25 (m, 4H), 7.22-7.16 (m, 4H), 5.96 (dd, J = 10.8 Hz, J = 17.4
Hz, 1H), 5.14 (dd, J = 1.1 Hz, J = 6.1 Hz, 1H), 5.21 (dd, J = 1.1
Hz, J = 12.7 Hz, 1H), 2.81-2.76 (m, 2H), 2.73-2.65 (m, 2H),
1.48 (s, 4H, overlapping CH3 and N-H peaks). 13C NMR (100
MHz, CDCl3): δ 146.2, 144.9, 140.1, 128.7, 128.3, 128.0, 126.4,
126.3, 126.0, 112.6, 60.4, 44.1, 37.0, 25.8. IR (neat): 3024.7,
2975.1, 2927.5, 2848.1, 1601.3, 1492.8, 1445.3, 1410.0, 1367.3
cm-1. HR MS (ESI+): calculated for [C18H22N]+ 252.1752, found
252.1765.
N-benzyl-2-phenylbut-3-en-2-amine (3a): yellow oil, 85%
1
yield. HNMR (300 MHz, CDCl3): δ 7.54 (d, J = 7.3 Hz, 2H),
7.37-7.31 (m, 6H), 7.25-7.21 (m, 2H), 6.10 (dd, J = 10.7 Hz, J =
17.5 Hz, 1H), 5.26 (dd, J = 1.0 Hz, J = 10.2 Hz, 1H), 5.21 (dd, J
= 1.0 Hz, J = 3.4 Hz, 1H), 3.61 (s, 2H), 1.58 (s, 3H), 1.50 (bs,
1H). 13C NMR (75 MHz, CDCl3): δ 146.5, 145.1, 141.5, 128.5,
128.4, 128.3, 126.9, 126.8, 126.7, 113.1, 60.9, 47.5, 26.3. IR
(neat): 3059.7, 3028.8, 2972.9, 2926.9, 2846.2, 1634.8, 1600.1,
1492.3, 1445.7, 1409.7, 1368.0 cm-1. HR MS (ESI+): calculated
for [C17H20N]+ 238.1596, found 238.1597.
2-(2-phenylbut-3-en-2-yl)-1,2,3,4-tetrahydroisoquinoline (3g):
1
yellow oil, 83% yield. H NMR (400 MHz, CDCl3): δ 7.59-7.56
(m, 2H), 7.33-7.29 (m, 2H), 7.24-7.20 (m, 1H), 7.10-7.08 (m,
3H), 7.00-6.98 (m, 1H), 6.10 (dd, J = 10.9 Hz, J = 17.6 Hz, 1H),
5.26 (dd, J = 1.2 Hz, J = 8.8 Hz, 1H), 5.23 (dd, J = 1.2 Hz, J =
15.5 Hz, 1H), 3.74 (s, 2H), 2.88-2.74 (m, 3H), 2.62-2.57 (m, 1H),
1.54 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 147.3, 142.8,
136.4, 135.4, 128.9, 128.4, 127.0, 126.8, 126.7, 126.0, 125.6,
114.4, 65.1, 49.4, 45.3, 30.6, 18.9. IR (neat): 3058.4, 3021.4,
2978.8, 2921.2, 2801.2, 2801.1, 1634.9, 1598.8, 1488.9, 1445.6,
1411.9 cm-1. HR MS (ESI+): calculated for [C19H22N]+ 264.1752,
found 264.1748.
N-(2-methylbenzyl)-2-phenylbut-3-en-2-amine (3b): yellow
oil, 74% yield. 1H NMR (300 MHz, CDCl3): δ 7.55 (d, J = 1.4
Hz, 1H), 7.52 (s, 1H), 7.36-7.30 (m, 3H), 7.25-7.22 (m, 1H),
7.18-7.12 (m, 3H), 6.10 (dd, J = 10.7 Hz, J = 17.5 Hz, 1H), 5.26
(dd, J = 1.0 Hz, J = 9.0 Hz, 1H), 5.22 (d, J = 0.8 Hz, 1H), 3.57
(d, J = 1.7 Hz, 2H), 2.31 (s, 3H), 1.59 (s, 3H), 1.32 (bs, 1H). 13
C

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5
2-phenyl-N-(1-phenylethyl)but-3-en-2-amine (3h): yellow oil,
81% yield % yield, 1:1 dr. 1H NMR (300 MHz, CDCl3): δ 7.59-
7.57 (m, 2H), 7.44-7.40 (m, 4H), 7.33-7.17 (m, 14H), 5.93 (ddd,
J = 9.0 Hz, J = 10.6 Hz, J = 17.5 Hz, 2H), 5.27 (dd, J = 10.7
Hz, J = 1.2 Hz, 1H), 5.18 (dd, J = 1.2 Hz, J = 10.0 Hz, 1H),
5.12 (dd, J = 1.1 Hz, J = 9.9 Hz, 1H), 5.04 (dd, J = 1.2 Hz, J =
10.6 Hz, 1H), 3.86 (q, J = 6.7 Hz, 1H), 3.68 (q, J = 6.7 Hz, 1H),
1.54 (bs, 2H), 1.36 (s, 3H), 1.28 (d, J = 6.8 Hz, 3H), 1.24 (d, J
= 6.7 Hz, 3H), 1.16 (s, 3H). 13C NMR (100 MHz, CDCl3): δ
149.5, 149.1, 148.5, 146.9, 144.7, 128.5, 128.4, 128.3, 128.2,
123.0, 126.9, 126.8, 126.77, 126.73, 126.6, 126.5, 126.4, 126.3,
113.5, 112.0, 62.0, 61.7, 53.0, 52.9, 27.5, 27.3, 26.7, 26.0. IR
(neat): 3083.9, 3059.1, 3023.8, 2970.8, 2923.7, 2863.7, 1600.0,
1491.1, 1445.1 cm-1. HR MS (ESI+): calculated for [C18H22N]+
252.1752, found 252.1752.
2-(4-bromophenyl)-N-(2-methylbenzyl)but-3-en-2-amine
(5d): yellow oil, 79% yield. 1H NMR (400 MHz, CDCl3): δ 7.46-
7.43 (m, 2H), 7.42-7.39 (m, 2H), 6.88 (d, J = 1.1 Hz, 1H), 6.78-
6.72 (m, 2H), 6.03 (ddd, J = 1.4 Hz, J = 6.9 Hz, J = 14.1 Hz,
1H), 5.93 (s, 2H), 5.24 (s, 1H), 5.21 (dd, J = 1.1 Hz, J = 6.9 Hz,
1H), 3.49 (s, 2H), 1.53 (s, 3H), 1.41 (bs, 1H). 13C NMR (100
MHz, CDCl3): δ 147.6, 146.3, 145.4, 144.2, 135.0, 131.2, 128.4,
120.9, 120.5, 113.4, 108.7, 108.0, 100.8, 60.4, 47.0, 26.1. IR
(neat): 2975.7, 2884.1, 1634.9, 1501.6, 1480.1, 1440.9 cm-1. HR
MS (ESI+): calculated for [C18H19BrNO2]+ 360.0599, found
360.0598.
2-(2-(4-bromophenyl)but-3-3n-2-yl)-1,2,3,4-
tetrahydroisoquinoline (5g) yellow oil, 88% yield. 1H NMR (400
MHz, CDCl3): δ 7.47-7.41 (m, 4H), 7.12-7.07 (m, 3H), 7.00-
6.98 (m, 1H), 6.05 (dd, J = 10.8 Hz, J = 17.6 Hz, 1H), 5.28 (dd,
J = 1.0 Hz, J = 10.8 Hz, 1H), 5.23 (dd, J = 1.0 Hz, J = 17.6 Hz,
1H), 3.72 (d, J = 2.0 Hz, 2H), 2.87-2.72 (m, 3H), 2.61-2.54 (m,
1H), 1.51 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 146.5, 142.1,
136.1, 135.2, 131.5, 128.9, 128.6, 126.9, 126.0, 125.6, 120.6,
114.9, 64.9, 49.4, 45.2, 30.5, 18.9. IR (neat): 2979.1, 2918.7,
2806.9, 1634.8, 1585.8, 1481.5, 1453.0 cm-1. HR MS (ESI+):
calculated for [C19H21BrN]+ 342.0857, found 342.0874.
N-benzyl-2-(4-phenoxyphenyl)but-3-en-2-amine (4a): yellow
1
oil, 85% yield. H NMR (300 MHz, CDCl3): δ 7.50 (d, J = 8.8
Hz, 2H), 7.37-7.28 (m, 6H), 7.24-7.22 (m, 1H), 7.08 (t, J = 7.4
Hz, 1H), 7.02-6.95 (m, 4H), 6.09 (dd, J = 10.7 Hz, J = 17.5
Hz, 1H), 5.26 (dd, J = 1.1 Hz, J = 10.5 Hz, 1H), 5.21 (dd, J =
1.1 Hz, J = 3.7 Hz, 1H), 3.26 (s, 2H), 1.63 (bs, 1H), 1.57 (s,
3H). 13C NMR (75 MHz, CDCl3): δ 157.5, 156.0, 145.1, 141.4,
141.3, 129.9, 128.5, 128.3, 128.2, 127.0, 123.3, 119.0, 118.6,
113.2, 60.6, 47.5, 26.4. IR (neat): 3059.7, 3027.5, 2971.6,
2926.2, 2851.9, 1588.1, 1504.0, 1488.5 cm-1. HR MS (ESI+):
calculated for [C23H24NO]+ 330.1858, found 330.1859.
1-(2-(4-bromophenyl)but-3-3n-2-yl)-4-methylpiperidine (5j)
yellow oil, 86% yield. H NMR (300 MHz, CDCl3): δ 7.40 (m,
1
4H), 5.96 (dd, J = 10.9 Hz, J = 17.6 Hz, 1H), 5.15-5.05 (m,
2H), 2.85 (ddd, J = 3.2 Hz, J = 5.8 Hz, J = 11.0 Hz, 1H), 2.65
(ddd, J = 3.2 Hz, J = 5.8 Hz, J = 10.8 Hz, 1H), 2.14-1.93 (m,
3H), 1.60-1.52 (m, 2H), 1.39 (s, 3H), 1.29-1.13 (m, 2H), 0.9 (d, J
= 6.2 Hz, 3H) . 13C NMR (100 MHz, CDCl3): δ 147.0, 143.8,
131.3, 128.6, 120.2, 113.5, 64.7, 47.6, 46.9, 35.6, 35.4, 31.6,
22.2, 17.9. IR (neat): 2947.8, 2916.9, 2868.6, 2801.0, 2841.6,
1635.0, 1586.7, 1485.5, 1454.9 cm-1. HR MS (ESI+): calculated
for [C16H23BrN]+ 308.1014, found 308.1004.
N-(2-methylbenzyl)-2-(4-phenoxyphenyl)but-3-en-2-amine
1
(4b): yellow oil, 88% yield. H NMR (300 MHz, CDCl3): δ 7.49
(d, J = 8.7 Hz, 2H), 7.35-7.29 (m, 3H), 7.16-7.13 (m, 3H), 7.08
(t, J = 7.3 Hz, 1H), 7.01-6.99 (m, 1H), 6.96 (d, J = 8.7 Hz, 2H),
6.09 (dd, J = 10.7 Hz, J = 17.5 Hz, 1H), 5.26 (d, J = 11.2 Hz,
1H), 5.22 (d, J = 4.3 Hz, 1H), 3.58 (d, J = 2.0 Hz, 2H), 2.31 (s,
3H), 1.59 (s, 3H), 1.32 (bs, 1H). 13C NMR (100 MHz, CDCl3): δ
157.5, 156.0, 145.2, 141.6, 139.3, 136.7, 130.4, 129.9, 128.8,
128.1, 127.1, 126.1, 123.3, 119.0, 118.6, 113.2, 60.5, 45.1, 26.0,
19.2. IR (neat): 2972.3, 1588.6, 1503.9, 1488.5, 1411.8 cm-1. HR
MS (ESI+): calculated for [C24H26NO]+ 344.2014, found
344.2028.
2-(2-(naphthalene-2-yl)but-3-en-2-yl)-1,2,3,4-
tetrahydroisoquinoline (6g): yellow oil, 73% yield. 1H NMR
(400 MHz, CDCl3): δ 7.90 (s, 1H), 7.85-7.77 (m, 4H), 7.47-7.41
(m, 2H), 7.14-7.07 (m, 3H), 6.99-6.97 (m, 1H), 6.22 (dd, J =
10.9 Hz, J = 17.5 Hz, 1H), 5.32 (dd, J = 1.1 Hz, J = 4.0 Hz,
1H), 5.28 (dd, J = 1.2 Hz, J = 10.6 Hz, 1H), 3.78(s, 2H), 2.87-
2.76 (m, 3H), 2.65 (m, 1H), 1.64 (s, 3H). 13C NMR (100 MHz,
N-(3-methoxybenzyl)-2-(4-phenoxyphenyl)but-3-en-2-amine
1
(4c): yellow oil, 76% yield. H NMR (400 MHz, CDCl3): δ 7.49
(d, J = 8.8 Hz, 2H), 7.35-7.30 (m, 2H), 7.24-7.20 (m, 1H), 7.10-
7.07 (m, 1H), 7.02-6.92 (m, 6H), 6.79-6.76 (m, 1H), 6.09 (dd, J
= 10.7 Hz, J = 17.5 Hz, 1H), 5.25 (dd, J = 1.2 Hz, J = 13.1
Hz, 1H), 5.21 (dd, J = 1.2 Hz, J = 6.3 Hz, 1H), 3.80 (s, 3H),
3.60 (d, J = 1.8 Hz, 2H), 1.57 (s, 3H). 13C NMR (100 MHz,
CDCl3): δ 159.6, 157.2, 155.8, 144.9, 142.9, 141.1, 129.6, 129.2,
127.9, 123.1, 120.3, 118.8, 118.3, 113.7, 112.9, 112.0, 60.3, 55.1,
47.2, 26.1. IR (neat): 2966.3, 2932.0, 2835.9, 1587.2, 1503.8,
1488.5, 1466.0, 1436.6 cm-1. HR MS (ESI+): calculated for
[C24H26NO2]+ 360.1964, found 360.1967.
CDCl3):
δ 144.9, 142.6, 136.4, 135.4, 133.6, 132.6, 128.9,
128.3, 128.1, 127.6, 127.0, 126.0, 125.8, 125.6, 125.6, 125.0,
114.7, 65.2, 49.5, 45.3, 30.6, 18.7. IR (neat): 3058.2, 2978.5,
2917.9, 2804.5, 1630.8, 1599.2, 1498.9, 1453.5, 1411.4 cm-1. HR
MS (ESI+): calculated for [C23H24N]+ 314.1909, found
314.1921.
4-methyl-1-(2-(naphthalene-2-yl)but-3-en-2-yl)piperidine (6j):
yellow solid, 84% yield, mp = 77-78 °C. H NMR (400 MHz,
1
CDCl3): δ 7.82-7.76 (m, 5H), 7.45-7.39 (m, 2H), 6.14 (dd, J =
10.9 Hz, J = 17.5 Hz, 1H), 5.18 (dd, J = 1.1 Hz, J = 4.4 Hz,
1H), 5.14 (dd, J = 1.1 Hz, J = 11.1 Hz, 1H), 2.93 (ddd, J = 3.1
Hz, J = 5.7 Hz, J = 10.9 Hz, 1H), 2.70 (ddd, J = 3.2 Hz, J = 5.8
Hz, J = 10.7 Hz, 1H), 2.13 (dt, J = 2.3 Hz, J = 11.2 Hz, 1H),
2.03 (td, J = 2.3Hz, J = 11.3 Hz, 1H), 1.60-1.56 (m, 1H), 1.53
(s, 3H), 1.34-1.18 (m, 4H), 0.91 (d, J = 6.2 Hz, 3H). 13C NMR
(100 MHz, CDCl3): δ 145.5, 144.2, 133.5, 132.4, 128.2, 127.8,
127.5, 125.8, 125.6, 124.8, 113.4, 65.0, 47.7, 47.0, 35.7, 35.5,
31.7, 22.2, 17.9. IR (neat): 3057.9, 2947.9, 2912.9, 2866.5,
2840.6, 2801.6, 1632.0, 1598.8, 1503.5, 1455.2, 1441.9, 1410.4
cm-1. HR MS (ESI+): calculated for [C20H26N]+ 280.2065, found
280.2066.
2-(4-phenoxyphenyl)-N(-thiophen-2-ylmethyl)but-3-en-2-
1
amine (4i): yellow oil, 73% yield. H NMR (400 MHz, CDCl3):
δ 7.46 (d, J = 8.7 Hz, 2H), 7.34-7.30 (m, 3H), 7.09 (t, J = 7.4
Hz, 1H), 7.00 (d, J = 8.3 Hz, 2H), 6.97 (d, J = 8.7 Hz, 2H), 6.29
(dd, J = 1.9 Hz, J = 2.9 Hz, 1H), 6.15 (d, J = 3.10 Hz, 1H), 6.06
(dd, J = 10.8 Hz, J = 17.4 Hz, 1H), 5.25 (dd, J = 6.4 Hz, 1H),
5.21 (s, 1H), 3.62 (s, 2H), 1.62 (s, 1H), 1.55 (s, 3H). 13C NMR
(100 MHz, CDCl3): δ 157.2, 155.8, 154.5, 144.3, 141.5, 140.5,
129.6, 127.9, 123.1, 118.8, 118.4, 113.2, 110.1, 106.1, 60.2, 40.4,
26.2. IR (neat): 2972.5, 2927.4, 1588.4, 1504.3, 1488.7 cm-1. HR
MS (ESI+): calculated for [C21H22NO2]+ 320.1651, found
320.1641.
N-(2-methylbenzyl)1-vinyl-1,2,3,4-tetrahydronaphthalen-1-
amine (7b): yellow oil, 78% yield. H NMR (400 MHz, CDCl3):
1

ACCEPTED MANUSCRIPT
6
Tetrahedron
δ 7.42 (dd, J = 1.6 Hz, J = 7.6 Hz, 1H), 7.33-7.31 (m, 1H),
Acknowledgments
7.20-7.09 (m, 6H), 6.04 (dd, J = 10.6 Hz, J = 17.3 Hz, 1H),
5.11 (dd, J = 1.4 Hz, J = 10.6 Hz, 1H), 4.92 (dd, J = 1.4 Hz, J
= 17.4 Hz, 1H), 3.63 (d, J = 12.3 Hz, 1H), 3.44 (d, J = 12.3 Hz,
1H), 2.88-2.74 (m, 2H), 2.31 (s, 3H), 2.20-2.14 (m, 1H), 1.94-
We thank the University of California at Irvine, the University
of Toronto, the National Science and Engineering Council of
Canada (NSERC), Roche, and Amgen for funding. V. M. D. is
grateful for an Eli Lilly Award.
1.82(m, 3H), 1.50 (bs, 1H). 13C NMR (100 MHz, CDCl3):
δ
146.2, 139.8, 139.3, 138.4, 136.7, 130.3, 129.2, 128.9, 128.5,
127.0, 126.7, 126.1, 125.9, 114.2, 60.6, 44.7, 33.2, 30.3, 19.9,
19.2. IR (neat): 3060.24, 3016.3, 2931.8, 2863.4, 1634.3, 1603.6,
1486.4, 1445.1 cm-1. HR MS (ESI+): calculated for [C20H24N]+
278.1909, found 278.1898.
References and notes
1. (a) Bach, R. D.; Dmitrenko, O. J. Am. Chem. Soc. 2006, 128,
4598. (b) Khoury, P. R.; Goddard, J. D.; Tam, W. Tetrahedron
2004, 60, 8103. (c) Fattahi, A.; McCarthy, R. E.; Ahmad, M. R.;
Kass, S. R. J. Am. Chem. Soc. 2003, 125, 11746. (d) Schleyer, P.
V. R.; Williams, J. E.; Blanchard, K. R. J. Am. Chem. Soc. 1970,
92, 2377. (e) Allen, F. H. Tetrahedron 1982, 38, 645.Goering, B.
K. Ph.D. Dissertation, Cornell University, 1995.
2. For recent reviews on cyclopropenes, see: (a) Zhu, Z.-B.; Wei, Y.;
Shi, M. Chem. Soc. Rev. DOI. (b) Rubin, M.; Rubina, M.;
Gevorgyan, V. Chem. Rev. 2007, 107, 3117. (c) Marek, I.;
Simaan, S.; Masarwa, A. Angew. Chem., Int. Ed. 2007, 46,
7364.Buchanan, J. G.; Sable, H. Z. In Selective Organic
Transformations; Thyagarajan, B. S., Ed.; Wiley-Interscience:
New York, 1972; Vol. 2, pp 1–95.
3. (a) Miege, F.; Meyer, C.; Cossy, J. J. Org. Chem. 2011, 7, 714. (b)
Miege, F.; Meyer, C.; Cossy, J. Angew. Chem., Int. Ed. 2011, 50,
5932. (c) Miege, F.; Meyer, C.; Cossy, J. Org. Lett. 2010, 12,
4144. (d) Hadfiled, M. S.; Bauer, J. T.; Glen, P. E.; Lee, A.-L.
Org. Biomol. Chem. 2010, 8, 4090. (e) Li, C.; Zeng, Y.; Wang, J.
Tetrahedron Lett. 2009, 50, 2956. (f) Bauer, J. T.; Hadfield, M.S.;
Lee, A.-L. Chem. Commun. 2008, 6405. (g) Zhu, Z.-B.; Shi, M.
Chem. Eur. J. 2008, 14, 10219. (h) Chuprakov, S.; Gevorgyan, V.
Org. Lett. 2007, 9, 4463. (i) Padwa, A.; Kassir, J. M.; Xu, S. L. J.
Org. Chem. 1997, 62, 1642. (j) Padwa, A.; Blacklock, T. J.; Loza,
R. J. Am. Chem. Soc. 1981, 103, 2404.
2-(1-vinyl-1,2,3,4-tetrahydronaphthalen-1-yl)-1,2,3,4-
tetrahydroisoquinoline (7g): yellow oil, 89% yield. 1H NMR
(400 MHz, CDCl3): δ 7.70 (dd, J = 1.8 Hz, J = 7.5 Hz, 1H),
7.17-7.04 (m, 5H), 6.96-6.94 (m, 1H), 6.03 (ddd, J = 0.7 Hz, J
= 10.9 Hz, J = 17.5 Hz, 1H), 5.16 (dd, J = 1.1 Hz, J = 3.8 Hz,
1H), 5.12 (dd, J = 1.1 Hz, J = 10.4 Hz, 1H), 3.86 (d, J = 14.7
Hz, 1H), 3.58 (d, J = 14.7 Hz, 1H), 2.82-2.73 (m, 4H), 2.64-
2.58 (m, 1H), 2.15-2.10 (m, 1H), 2.04-1.92 (m, 2H), 1.91-1.80
(m, 2H). 13C NMR (100 MHz, CDCl3): δ 145.1, 140.6, 138.3,
136.6, 135.5, 129.0, 128.9, 126.9, 126.47, 126.43, 125.9, 125.5,
113.7, 64.3, 49.2, 44.7, 30.6, 30.5, 23.7, 21.0. IR (neat): 3060.5,
3016.2, 2931.8, 2865.3, 2801.5, 2741.9, 1633.8, 1484.9, 1447.4
cm-1. HR MS (ESI+): calculated for [C21H24N]+ 290.1909, found
290.1906.
N-(2-methylbenzyl)-2-(thiophen-2-yl)but-3-en-2-amine
(8b)
1
yellow oil, 74% yield. H NMR (400 MHz, CDCl3): δ 7.35-7.33
(m, 1H), 7.21 (dd, J = 1.3 Hz, J = 4.8 Hz, 1H), 7.17-7.12 (m,
3H), 6.96-6.94 (m, 2H), 6.15 (dd, J = 10.6 Hz, J = 17.3 Hz,
1H), 5.28 (d, J = 17.4 Hz, 1H), 5.20 (d, J = 10.6 Hz, 1H), 3.64
(s, 2H), 2.33 (s, 3H), 1.68 (s, 3H), 1.51 (bs, 1H). 13C NMR (75
MHz, CDCl3): δ 152.9, 144.6, 138.9, 136.8, 130.3, 128.9, 127.1,
126.6, 126.1, 124.4, 123.8, 113.4, 59.6, 45.2, 27.1, 19.2. IR
(neat): 3068.3, 3016.7, 2970.5, 2924.0, 2851.3, 1635.43, 1490.0,
1460.63, 1408.7 cm-1. HR MS (ESI+): calculated for
[C16H20NS]+ 258.1316, found 258.1310.
4. This intermediate was proposed to arise either from an attack on
the cyclopropene π-bond on the silver ion followed by a rapid ring
opening of the transient cyclopropyl cation or directly from the σ-
bond attack of the cyclopropene at the metal ion.
5. Intramolecular trappings of the Rh- and Cu-carbenoids with
pyridyl nitrogen nuclephiles has been reported by Gevorgyan, see
reference 3h.
6. Nakamura, I.; Bajracharya, G. B.; Yamamoto, Y. J. Org. Chem.
2003, 68, 2297.
7. Giner, X.; Najera, C. Synlett. 2009, 19, 3211.
N-benzyl-4-(tert-butyl)-1-vinylcyclohexanamine (9a): 69%
combined yields, 2.8:1 dr.
8. For recent reviews on gold-mediated hydroamination reactions,
see: (a) Krause, N.; Winter, N. Chem. Rev. 2011, 111, 1994. (b)
Furstner, A. Chem. Soc. Rev. 2009, 38, 3208.
9. For discussion into the nature of gold carbene vs. cationic
intermediates, see: (a) Seidel, G.; Mynott, R.; Furstner, A. Angew.
Chem, Int. Ed. 2009, 48, 2510. (b) Benitez, D. N.; Shapiro, N. D.;
Tkatchouk, E.; Wang, Y.; Goddard, W. A., III; Toste, F. D. Nat.
Chem. 2009, 1, 482.
10. For reviews on Ag-catalyzed reactions, see: (a) Corral-Alvarez,
M.; Munoz-Dorado, M.; Garcia-Rodriguez, I. Chem. Rev. 2008,
108, 3174. (b) Yamamoto, Y. Chem. Rev. 2008, 108, 3199. (c)
Weibel, J.-M; Blanc, A.; Pale, P. Chem. Rev. 2008, 108, 3139. (d)
Harmata, M. Silver in Organic Chemistry; Wiley, New Jersey,
2010.
11. For reviews on chiral anion-mediated asymmetric ion pairing
chemistry, see: (a) Lacour, J.; Moraleda, D. Chem. Commun.
2009, 7073. (b) Lacour, J.; Hebbe-Vition, V. Chem. Soc. Rev.
2003, 32, 373.
9a-major isomer: colourless oil, 51% yield. 1H NMR (400
MHz, CDCl3): δ 7.37-7.36 (m, 2H), 7.33-7.29 (m, 2H), 7.25-
7.21 (m, 1H), 5.79 (dd, J = 10.8 Hz, J = 17.6 Hz, 1H), 5.09 (d,
J = 9.9 Hz, J = 1.5 Hz, 1H), 5.06 (dd, J = 1.5 Hz, J = 3.1 Hz,
1H), 3.54 (s, 2H), 1.81-1.79 (m, 2H), 1.58-1.56 (m, 2H), 1.41-
1.35 (m, 4H), 1.23 (bs, 1H), 1.03-0.95 (m, 1H), 0.87 (s, 9H). 13
C
NMR (75 MHz, CDCl3): δ 146.93, 141.82, 128.28, 128.19,
126.64, 111.69, 55.21, 47.77, 46.24, 34.80, 32.47, 27.59, 21.91.
IR (neat): 2930.2, 2863.0, 1635.0, 1495.4, 1452.7, 1412.1,
1393.1, 1364.9 cm-1. HR MS (ESI+): calculated for [C19H30N]+
272.2372, found 272.2363.
9a-minor isomer: colourless oil, 18% yield. 1H NMR (400
MHz, CDCl3): δ 7.32-7.29 (m, 3H), 7.27-7.26 (m, 1H), 7.23-
7.19 (m, 1H), 5.60 (dd, J = 10.9 Hz, J = 17.8 Hz, 1H), 5.33 (dd, J
= 10.9 Hz, J = 1.4 Hz, 1H), 5.15 (dd, J = 1.4 Hz, J = 17.8
Hz, 1H), 3.43 (s, 2H), 1.98-1.94 (m, 2H), 1.65-1.62 (m, 2H),
1.54 (bs, 1H), 1.45-1.38 (m, 2H), 1.14 (m, 2H), 1.06-0.99 (m,
1H), 0.83 (s, 9H).13C NMR (100 MHz, CDCl3): δ 142.1, 128.3,
128.1, 126.7, 115.4, 56.9, 48.2, 46.3, 36.9, 32.3, 27.6, 27.5, 23.8.
IR (neat): 2930.5, 2853.9, 1670.4, 1495.1, 1453.3, 1408.1,
1393.4, 1365.1 cm-1. HR MS (ESI+): calculated for [C19H30N]+
272.2372, found 272.2379.
Supplementary Material
Supplementary data associated with this article can be found
1
at. These data include the substrate preparation, IR, HR MS, H
NMR and 13C NMR spectra for all new compounds.

ACCEPTED MANUSCRIPT
Silver-Catalyzed Ring-Opening of Cyclopropenes: Preparation of 3° α-
Branched Allylic Amines
Diem H. T. Phan, Vy M. Dong*
Department of Chemistry, University of California at Irvine, Irvine, CA, 92697-2025, USA
*dongv@uci.edu
Supporting Information
Contents
1 Experimental ...............................................................................................................................2
1.1 General Considerations........................................................................................................2
1.2 Synthesis of Cyclopropenes.................................................................................................3
1.2.1 Preparations of 1,1-disubstituted alkenes ................................................................3
1.2.2 Synthesis of bromocyclopropanes ...........................................................................4
1.2.3 Synthesis of cyclopropenes......................................................................................5
1.2.4 AgOTf-catalyzed hydroamination of cyclopropenes...............................................6
1.3 NMR Spectra .....................................................................................................................14

ACCEPTED MANUSCRIPT
2
1
Experimental
General Considerations
1.1
Commercial reagents were purchased from Sigma Aldrich, Strem, Alfa Aesar, and Acros and
used without further purification. All reactions were carried out under an argon atmosphere
unless otherwise indicated. Toluene used in the silver-catalyzed hydroamination reaction was
dried through two columns of activated alumina and then distilled over CaH2. Reactions were
monitored using thin-layer chromatography (TLC) on EMD Silica Gel 60 F254 plates.
Visualization of the developed plates was performed under UV light (254 nm) or KMnO4 stain.
Column chromatography was performed with Silicycle Silia-P Flash Silica Gel, using either
glass columns or a Biotage SP-1 system. Organic solutions were concentrated under reduced
1
pressure on a Büchi rotary evaporator. H and 13C NMR spectra were recorded on a Varian
Mercury 300, Varian Mercury 400, Bruker 400 or a VRX-S (Unity) 400 spectrometer. NMR
1
spectra were internally referenced to the residual solvent signal (TMS). Data for H NMR are
reported as follows: chemical shift (δ ppm), multiplicity (s = singlet, d = doublet, t = triplet, q =
13
quartet, m = multiplet, br = broad), coupling constant (Hz), integration. Data for C NMR are
reported in chemical shift (δ ppm).
High resolution mass spectra (HRMS) were obtained on a micromass 70S-250 spectrometer (EI)
or an ABI/Sciex Qstar Mass Spectrometer (ESI). Infrared (IR) spectra were obtained on a
Perkin-Elmer Spectrum 1000 FT-IR Systems and are reported in terms of frequency of
absorption (cm-1). Melting point ranges were determined on a Fisher-Johns Melting Point
Apparatus. Enantiomeric excess was determined by gas chromatography using a Perkin-Elmer
Autosystem XL chromatography with a chiral column (CP chirasil-Dex CB 25 m x 2.5 mm).
Hydrogem was used as a mobile phase at a column pressure of 5 psi. The injector temperature
was 250 °C, a FID temperature was 275 °C, and an oven temperature was 130 °C.

ACCEPTED MANUSCRIPT
3
1.2
Synthesis of Cyclopropenes
General Scheme for the Preparation of Cyclopropenes
1.2.1
Preparations of 1,1-disubstituted alkenes
General Procedure: According to previously reported procedure,1 bromoform (20mmol, 2 molar
eq) was added to vigorously stirred alkene (10mmol), followed by the phase transfer catalyst
(1mmol, 0.1 molar eq) and the 50% aqueous solution of NaOH (25mmol, 2.5 eq). The mixture
was stirred at 70 °C for one day, then quenched with 10% aq. HCl and extracted with DCM (3
times). The combined organic layers were washed with water and brine, then dried with Na2SO4,
filtered and concentrated under reduced pressure. Flash column chromatography of the resulting
residue on silica gel (eluent- hexane) gave the dibromocyclopropane products.
1-(2,2-dibromo-1-methylcyclopropyl)-4-phenoxybenze (4-II): yellow
solid, 47% yield, mp = 52-53 °C. 1H NMR (400 MHz, CDCl3) δ 7.31 (dd, J
= 8.5 Hz, J = 7.5 Hz, 2H), 7.23 (d, J = 8.7 Hz, 2H), 7.09 (t, J = 7.4 Hz, 1H),
7.00 (dd, J = 1.1 Hz, J = 8.6 Hz, 2H), 6.96 (d, J = 8.8 Hz, 2H), 2.11 (d, J =
13
8.8 Hz, 1H), 1.74 (d, J = 8.7 Hz, 1H), 1.69 (s, 3H). C NMR (100 MHz,
CDCl3): δ 157.2, 156.6, 137.3, 130.09, 130.07, 123.7, 119.3, 118.7, 37.2, 35.4, 34.1, 27.9. IR
(neat): 2984.7, 1606.7, 1588.0, 1506.0, 1486.4, 1231.5 cm-1. HR MS (ESI+): calculated for
[C16H15Br2O]+ 380.9490, found 380.9491.
1 Phan, D. H. T.; Kou, K. G. M.; Dong, V. M. J. Am. Chem. Soc. 2010, 132, 16354.

ACCEPTED MANUSCRIPT
4
1-bromo-4-(2,2-dibromo-1-methylcyclopropyl)benzene (5-II): pale yellow
oil, 91% yield, colourless oil, 91% yield. 1H NMR (400 MHz, CDCl3) δ 7.46
(d, J = 8.6 Hz, 2H), 7.16 (d, J = 8.5 Hz, 2H), 2.09 (d, J = 7.7 Hz, 1H), 1.76 (d,
13
J = 7.6 Hz, 1H), 1.66 (s, 3H). C NMR (100 MHz, CDCl3): δ 141.6, 131.8,
130.5, 121.5, 36.3, 35.5, 34.0, 27.9.
1.2.2
Synthesis of bromocyclopropanes
General procedure: bromocyclopropanes (10mmol) were prepared by partial reduction of the
corresponding dibromocyclopropanes with EtMgBr (13mmol, 1.3 molar eq) in the presence of
Ti(OiPr)4 (1mmol, 0.1 molar eq) according to the published protocol.1 Ethylmagnesium bromide
was added dropwise to a stirring solution of the dibromocyclopropane and Ti(OiPr)4 in
anhydrous ether under argon and in an ice-bath. The mixture turned dark orange instantly with
generation of heat (fast addition of the Grignard reagent should be avoided to prevent
evaporation of solvent). The reaction mixture was stirred at rt for 4 h, then quenched with 10%
aq. HCl. The organic phase was separated and the aqueous layer was extracted twice with ether.
The combined ethereal layers were washed consecutively with sat. NaHCO3 and brine, then
dried with Na2SO4, filtered and concentrated under reduced pressure. The product was purified
by flash column chromatography on silica gel (eluent-hexanes) to afford the bromocyclopropane
as a mixture of diastereomers.
1-(2-bromo-1-methylcyclopropyl)-4-phenoxybenzene (4-I):
colourless
1
oil, quantitative yield, as a 2:1 mixture of the trans:cis products. H NMR
(400 MHz, CDCl3, all the peaks are integrated relatively based on the cis
methine proton) δ 7.29 (t, J = 7.7 Hz, 6H), 7.24 (d, J = 8.1 Hz, 2H), 7.16 (d,
J = 8.3 Hz, 4H), 7.06 (t, J = 10.8 Hz, 3H), 7.01-6.95 (m, 8H), 6.91 (d, J = 7.9 Hz, 4H), 3.17 (dd,
J = 4.8 Hz, J = 7.8 Hz, 2H trans methine proton), 3.04 (t, J = 5.9 Hz, 1H cis methine proton),
1.58 (s, 6H, trans Me), 1.60-1.57 (m, 2H, trans methylene proton) 1.41 (s, 3H, cis Me), 1.32 (d, J
13
= 6.3 Hz, 2H), 1.04-1.01 (m, 2H). C NMR (100 MHz, CDCl3): δ 224.9, 157.5, 156.2, 156.0,
139.5, 137.3, 130.9, 130.0, 129.9, 128.6, 128.4, 123.5, 119.2, 119.2, 119.0, 118.8, 118.7, 30.7,
28.7, 27.3, 27.3, 25.5, 24.4, 23.6, 22.5. IR (neat): 2959.3, 1589.1, 1508.0, 1488.6 cm-1. HR MS
(ESI+): calculated for [C16H16BrO]+ 303.0385, found 303.0389.

ACCEPTED MANUSCRIPT
5
1-bromo-4-(2-bromo-1-methylcyclopropyl)benzene (5-I): colourless oil,
quantitative yield, as a 1.5:1 mixture of the trans:cis products. All the peaks
are integrated relatively based on the cis-methine proton. 1H NMR (400 MHz,
CDCl3) δ 7.47 (d, J = 8.5 Hz, 1.7H), 7.41 (d, J = 8.5 Hz, 2.9H), 7.12 (d, J =
8.5 Hz, 1.7H), 7.11 (d, J = 8.5 Hz, 2.9H), 3.17 (dd, J = 4.8 Hz, J = 8.0 Hz, 1.5H trans methine
proton), 3.07 (dd, J = 4.4 Hz, J = 7.4 Hz, 1H cis methine proton), 1.63-1.57 (m, 2H), 1.58 (s,
4.5H, trans-Me), 1.43 (s, 3H, cis-Me), 1.39-1.33 (m, 2.9H), 1.07 (dd, J = 4.8 Hz, J = 6.5 Hz, 2.8
13
H). C NMR (100 MHz, CDCl3): δ 143.7, 141.4, 131.8, 131.5, 131.4, 129.0, 120.5, 30.2, 28.0,
26.9, 25.6, 24.0, 23.5, 22.4. IR (neat): 2960.4, 2924.6, 1489.9, 1434.4, 1394.1 cm-1.
1.2.3
Synthesis of cyclopropenes
General procedure: A solution of bromocyclopropane (5mmol) in DMSO was added to a stirring
solution of potassium t-butoxide (6.5mmol, 1.3 molar eq) in DMSO. The mixture turned dark
brown instantly and was stirred at rt overnight. It was then quenched with 10% aq. HCl and
extracted with ether. The ethereal layers were combined, washed with brine, dried with Na2SO4,
filtered, and concentrated in vacuo. Flash column chromatography of the residue on silica gel
(eluent-hexane) afforded the cyclopropene product.
1-(1-methylcyloprop-2-2n-1-yl)-4-phenoxybenzene (4): colourless oil, 52%
PhO
1
yield. H NMR (400 MHz, CDCl3): δ 7.45-7.41 (m, 2H), 7.38 (s, 2H), 7.33-
Me
13
7.30 (m, 2H), 7.21-7.18 (m, 1H), 7.15-7.09 (m, 4H), 1.79 (s, 3H). C NMR
(100 MHz, CDCl3): δ 158.2, 154.8, 145.4, 130.0, 127.6, 123.1, 119.0, 118.7,
116.1, 26.0, 21.8. IR (neat): 3747.8, 2923.5, 1637.8, 1588.8, 1505.3, 1488.4 cm-1. HR MS
(ESI+): calculated for [C16H15O]+ 223.1123, found 223.1129.
1-bromo-4-(1-methylcycloprop-2-en-1-yl)benzene (5): white semi-solid, 58%
1
yield. H NMR (300 MHz, CDCl3): δ 7.38 (d, J = 8.5 Hz, 2H), 7.23 (s, 2H),
13
7.06 (d, J = 8.5 Hz, 2H), 1.59 (s, 3H). C NMR (100 MHz, CDCl3): δ 149.3,
131.0, 128.2, 119.1, 115.6, 25.6, 21.8. IR (neat): 2970.3, 2947.2, 2863.6,
1640.2, 1489.2, 1395.7 cm-1. HR MS (ESI+): calculated for [C10H10Br]+ 208.9966, found
208.9962.

ACCEPTED MANUSCRIPT
6
1.2.4
AgOTf-catalyzed hydroamination of cyclopropenes
General Procedure: In a flame-dried 1 dram vial containing a stir bar, silver triflate (10.3 mg,
0.4 mmol, 20mol %) was dissolved in 0.1 ml of anhydrous toluene. Amine (0.2 mmol) was then
added to the reaction vial via a micropipette, followed by cyclopropene (0.4 mmol, 2 molar
equivalents). The reaction vial was then capped and stirred at 70 °C for 1 day (unless indicated
otherwise). The reaction mixture was then cooled down to room temperature and the silver
catalyst was removed by passing the reaction crude through a silica gel pipette plug using 10mL
of EtOAc as the eluent. The resulting organic solvents were concentrated in vacuo. The allylic
amine product 3 was isolated by preparative thin layer chromatography (2 plates, 3 elutions). The
allylic amine:indene ratios were determined by 1H NMR analysis of the crude reaction mixtures.
The ees were determined by chiral GC analysis of the products after purification by silica gel
chromatography.
1
N-benzyl-2-phenylbut-3-en-2-amine (3a): yellow oil, 85% yield. H
NMR (300 MHz, CDCl3): δ 7.54 (d, J = 7.3 Hz, 2H), 7.37-7.31 (m, 6H),
N
Me
7.25-7.21 (m, 2H), 6.10 (dd, J = 10.7 Hz, J = 17.5 Hz, 1H), 5.26 (dd, J =
H
1.0 Hz, J = 10.2 Hz, 1H), 5.21 (dd, J = 1.0 Hz, J = 3.4 Hz, 1H), 3.61 (s,
2H), 1.58 (s, 3H), 1.50 (bs, 1H). 13C NMR (75 MHz, CDCl3): δ 146.5, 145.1, 141.5, 128.5,
128.4, 128.3, 126.9, 126.8, 126.7, 113.1, 60.9, 47.5, 26.3. IR (neat): 3059.7, 3028.8, 2972.9,
2926.9, 2846.2, 1634.8, 1600.1, 1492.3, 1445.7, 1409.7, 1368.0 cm-1. HR MS (ESI+): calculated
for [C17H20N]+ 238.1596, found 238.1597.
AgP*-catalyzed hydroamination of cyclopropenes
The chiral silver salt AgP* was prepared from the corresponding phosphoric
acid
(R)-3,3´-bis(2,4,6-triisopropylphenyl)-1,1´-binaphthyl-2,2´-
diylhydrogenphosphate, reported by List (J. Seayad, A. M. Seayad, B. List,
J. Am. Chem. Soc. 2006, 128, 1086)
The reaction was set up in the same protocol as described above but at a smaller scale (0.1 mmol
of benzylamine 2a, 0.2 mmol of cyclopropene 1, 0.02 mmol of AgP*, 0.1mL of toluene, heated
at 70 ° C for 1 day). The product 3a was purified by preparative thin layer chromatography

ACCEPTED MANUSCRIPT
7
(eluent: 3% EtOAc in hexanes, multiple elutions, 73% yield). Enantiomeric excess of the product
3a was determined by gas chromatography using a Perkin-Elmer Autosystem XL
chromatography with a chiral column (CP chirasil-Dex CB 25 m x 2.5 mm). Hydrogen was used
as a mobile phase at a column pressure of 5 psi. The injector temperature was 250 °C, the FID
temperature was 275 °C, and the oven temperature was 130 °C. GC retention times: tmajor = 139
min, tminor = 141min, 9% ee.
N-(2-methylbenzyl)-2-phenylbut-3-en-2-amine (3b): yellow oil, 74%
Me
1
yield. H NMR (300 MHz, CDCl3): δ 7.55 (d, J = 1.4 Hz, 1H), 7.52 (s,
N
Me
1H), 7.36-7.30 (m, 3H), 7.25-7.22 (m, 1H), 7.18-7.12 (m, 3H), 6.10 (dd,
H
J = 10.7 Hz, J = 17.5 Hz, 1H), 5.26 (dd, J = 1.0 Hz, J = 9.0 Hz, 1H), 5.22
(d, J = 0.8 Hz, 1H), 3.57 (d, J = 1.7 Hz, 2H), 2.31 (s, 3H), 1.59 (s, 3H), 1.32 (bs, 1H). 13C NMR
(100 MHz, CDCl3): δ 146.7, 145.2, 139.3, 136.8, 130.3, 128.8, 128.3, 127.0, 126.8, 126.7, 126.1,
113.2, 60.9, 45.1, 26.0, 19.2. IR (neat): 3059.7, 3021.9, 2924.7, 2973.6, 1634.1, 1600.7, 1490.0,
1445.6, 1367.2 cm-1. HR MS (ESI+): calculated for [C18H22N]+ 252.1752, found 252.1757.
N-(3-methoxybenzyl)-2-phenylbut-3-en-2-amine (3c): yellow
1
oil, 74% yield. H NMR (300 MHz, CDCl3): δ 7.55-7.52 (m, 2H),
OMe
N
Me
7.40-7.31 (m, 3H), 7.25-7.19 (m, 2H), 6.95 (s, 1H), 6.79-6.76 (m,
H
1H), 6.09 (dd, J = 10.7 Hz, J = 17.5 Hz, 1H), 5.25 (dd, J = 1.1 Hz,
J = 10.6 Hz, 1H), 5.21 (dd, J = 1.1 Hz, J = 3.7 Hz, 1H), 3.80 (s, 3H), 3.59 (s, 2H), 1.57 (s, 3H),
13
1.55 (bs, 1H). C NMR (75 MHz, CDCl3): δ 159.9, 146.5, 145.1, 143.2, 129.5, 128.4, 126.8,
126.7, 125.9, 120.6, 113.9, 113.2, 112.3, 60.9, 55.4, 47.4, 26.3. IR (neat): 3056.7, 2970.8,
2834.3, 1599.6, 1585.3, 1489.0, 1445.7, 1263.2 cm-1. HR MS (ESI+): calculated for [C18H22NO]+
268.1701, found 268.1695.
N-(benzo[d][1,3]dioxo-5-ylmethyl)-2-phenylbut-3-en-2-amine
1
(3d): yellow oil, 71% yield. H NMR (400 MHz, CDCl3): δ 7.54-
7.53 (m, 1H), 7.51 (d, J = 1.1 Hz, 1H), 7.34 (t, J = 7.6 Hz, 2H),
7.25-7.21 (m, 1H), 6.89 (d, J = 1.4 Hz, 2H), 6.76 (dd, J = 16.6 Hz, J
= 4.7 Hz, 1H), 6.08 (dd, J = 10.6 Hz, J = 17.6 Hz, 1H), 5.92 (s, 2H), 5.24 (dd, J = 1.2 Hz, J = 9.6

ACCEPTED MANUSCRIPT
8
Hz, 1H), 5.20 (dd, J = 1.1 Hz, J = 2.8 Hz, 1H), 3.50 (d, J = 2.3 Hz, 2H), 1.56 (s, 3H), 1.53 (bs,
1H). 13C NMR (100 MHz, CDCl3): δ 147.5, 146.3, 146.2, 144.8, 135.3, 128.1, 126.5, 126.5,
120.9, 112.9, 108.7, 108.0, 100.8, 60.6, 47.0, 26.1. IR (neat): 2976.3, 2883.7, 1713.5, 1689.0,
1602.2, 1502.2, 1488.4, 1441.6, 1362.9, 1248.2 cm-1. HR MS (ESI+): calculated for
[C18H20NO2]+ 282.1494, found 282.1486.
N-(3-chlorobenzyl-2-phenylbut-3-en-2-amine (3e): yellow oil, 67%
1
yield. H NMR (300 MHz, CDCl3): δ 7.54-7.51 (m, 2H), 7.38-7.32
(m, 3H), 7.26-7.19 (m, 4H), 6.08 (dd, J = 10.8 Hz, J = 17.4 Hz, 1H),
5.26 (dd, J = 0.9 Hz, J = 7.6 Hz, 1H), 5.21 (s, 1H), 3.58 (s, 2H), 1.56
(s, 4H, overlapping CH3 and N-H peaks). 13C NMR (75 MHz, CDCl3): δ 146.2, 144.9, 143.7,
134.3, 129.7, 128.4, 128.3, 127.1, 126.9, 126.7, 126.4, 113.3, 60.9, 47.0, 26.3. IR (neat): 3059.4,
2970.9, 2928.2, 2847.9, 1635.9, 1598.0, 1574.7, 1490.3, 1445.4, 1410.1 cm-1. HR MS (ESI+):
calculated for [C17H19ClN]+ 272.1206, found 272.1201.
N-phenethyl-2-phenylbut-3-en-2-amine (3f): yellow oil, 67% yield.
1H NMR (300 MHz, CDCl3): δ 7.37-7.34 (m, 2H), 7.31-7.25 (m, 4H),
7.22-7.16 (m, 4H), 5.96 (dd, J = 10.8 Hz, J = 17.4 Hz, 1H), 5.14 (dd, J
= 1.1 Hz, J = 6.1 Hz, 1H), 5.21 (dd, J = 1.1 Hz, J = 12.7 Hz, 1H), 2.81-2.76 (m, 2H), 2.73-2.65
13
(m, 2H), 1.48 (s, 4H, overlapping CH3 and N-H peaks). C NMR (100 MHz, CDCl3): δ 146.2,
144.9, 140.1, 128.7, 128.3, 128.0, 126.4, 126.3, 126.0, 112.6, 60.4, 44.1, 37.0, 25.8. IR (neat):
3024.7, 2975.1, 2927.5, 2848.1, 1601.3, 1492.8, 1445.3, 1410.0, 1367.3 cm-1. HR MS (ESI+):
calculated for [C18H22N]+ 252.1752, found 252.1765.
2-(2-phenylbut-3-en-2-yl)-1,2,3,4-tetrahydroisoquinoline (3g): yellow
1
oil, 83% yield. H NMR (400 MHz, CDCl3): δ 7.59-7.56 (m, 2H), 7.33-
7.29 (m, 2H), 7.24-7.20 (m, 1H), 7.10-7.08 (m, 3H), 7.00-6.98 (m, 1H),
6.10 (dd, J = 10.9 Hz, J = 17.6 Hz, 1H), 5.26 (dd, J = 1.2 Hz, J = 8.8 Hz,
1H), 5.23 (dd, J = 1.2 Hz, J = 15.5 Hz, 1H), 3.74 (s, 2H), 2.88-2.74 (m, 3H), 2.62-2.57 (m, 1H),
13
1.54 (s, 3H). C NMR (100 MHz, CDCl3): δ 147.3, 142.8, 136.4, 135.4, 128.9, 128.4, 127.0,
126.8, 126.7, 126.0, 125.6, 114.4, 65.1, 49.4, 45.3, 30.6, 18.9. IR (neat): 3058.4, 3021.4, 2978.8,

ACCEPTED MANUSCRIPT
9
2921.2, 2801.2, 2801.1, 1634.9, 1598.8, 1488.9, 1445.6, 1411.9 cm-1. HR MS (ESI+): calculated
for [C19H22N]+ 264.1752, found 264.1748.
2-phenyl-N-(1-phenylethyl)but-3-en-2-amine (3h): yellow oil, 81%
yield % yield, 1:1 dr. 1H NMR (300 MHz, CDCl3): δ 7.59-7.57 (m, 2H),
7.44-7.40 (m, 4H), 7.33-7.17 (m, 14H), 5.93 (ddd, J = 9.0 Hz, J = 10.6
Hz, J = 17.5 Hz, 2H), 5.27 (dd, J = 10.7 Hz, J = 1.2 Hz, 1H), 5.18 (dd, J
= 1.2 Hz, J = 10.0 Hz, 1H), 5.12 (dd, J = 1.1 Hz, J = 9.9 Hz, 1H), 5.04 (dd, J = 1.2 Hz, J = 10.6
Hz, 1H), 3.86 (q, J = 6.7 Hz, 1H), 3.68 (q, J = 6.7 Hz, 1H), 1.54 (bs, 2H), 1.36 (s, 3H), 1.28 (d, J
13
= 6.8 Hz, 3H), 1.24 (d, J = 6.7 Hz, 3H), 1.16 (s, 3H). C NMR (100 MHz, CDCl3): δ 149.5,
149.1, 148.5, 146.9, 144.7, 128.5, 128.4, 128.3, 128.2, 123.0, 126.9, 126.8, 126.77, 126.73, 126.6,
126.5, 126.4, 126.3, 113.5, 112.0, 62.0, 61.7, 53.0, 52.9, 27.5, 27.3, 26.7, 26.0. IR (neat): 3083.9,
3059.1, 3023.8, 2970.8, 2923.7, 2863.7, 1600.0, 1491.1, 1445.1 cm-1. HR MS (ESI+): calculated
for [C18H22N]+ 252.1752, found 252.1752.
N-benzyl-2-(4-phenoxyphenyl)but-3-en-2-amine (4a): yellow oil,
85% yield. 1H NMR (300 MHz, CDCl3): δ 7.50 (d, J = 8.8 Hz, 2H),
7.37-7.28 (m, 6H), 7.24-7.22 (m, 1H), 7.08 (t, J = 7.4 Hz, 1H),
7.02-6.95 (m, 4H), 6.09 (dd, J = 10.7 Hz, J = 17.5 Hz, 1H), 5.26
(dd, J = 1.1 Hz, J = 10.5 Hz, 1H), 5.21 (dd, J = 1.1 Hz, J = 3.7 Hz, 1H), 3.26 (s, 2H), 1.63 (bs,
1H), 1.57 (s, 3H). 13C NMR (75 MHz, CDCl3): δ 157.5, 156.0, 145.1, 141.4, 141.3, 129.9, 128.5,
128.3, 128.2, 127.0, 123.3, 119.0, 118.6, 113.2, 60.6, 47.5, 26.4. IR (neat): 3059.7, 3027.5,
2971.6, 2926.2, 2851.9, 1588.1, 1504.0, 1488.5 cm-1. HR MS (ESI+): calculated for [C23H24NO]+
330.1858, found 330.1859.
N-(2-methylbenzyl)-2-(4-phenoxyphenyl)but-3-en-2-amine (4b):
1
yellow oil, 88% yield. H NMR (300 MHz, CDCl3): δ 7.49 (d, J =
8.7 Hz, 2H), 7.35-7.29 (m, 3H), 7.16-7.13 (m, 3H), 7.08 (t, J = 7.3
Hz, 1H), 7.01-6.99 (m, 1H), 6.96 (d, J = 8.7 Hz, 2H), 6.09 (dd, J =
10.7 Hz, J = 17.5 Hz, 1H), 5.26 (d, J = 11.2 Hz, 1H), 5.22 (d, J = 4.3 Hz, 1H), 3.58 (d, J = 2.0
Hz, 2H), 2.31 (s, 3H), 1.59 (s, 3H), 1.32 (bs, 1H). 13C NMR (100 MHz, CDCl3): δ 157.5, 156.0,
145.2, 141.6, 139.3, 136.7, 130.4, 129.9, 128.8, 128.1, 127.1, 126.1, 123.3, 119.0, 118.6, 113.2,

ACCEPTED MANUSCRIPT
10
60.5, 45.1, 26.0, 19.2. IR (neat): 2972.3, 1588.6, 1503.9, 1488.5, 1411.8 cm-1. HR MS (ESI+):
calculated for [C24H26NO]+ 344.2014, found 344.2028.
N-(3-methoxybenzyl)-2-(4-phenoxyphenyl)but-3-en-2-
1
amine (4c): yellow oil, 76% yield. H NMR (400 MHz,
CDCl3): δ 7.49 (d, J = 8.8 Hz, 2H), 7.35-7.30 (m, 2H), 7.24-
7.20 (m, 1H), 7.10-7.07 (m, 1H), 7.02-6.92 (m, 6H), 6.79-
6.76 (m, 1H), 6.09 (dd, J = 10.7 Hz, J = 17.5 Hz, 1H), 5.25 (dd, J = 1.2 Hz, J = 13.1 Hz, 1H),
13
5.21 (dd, J = 1.2 Hz, J = 6.3 Hz, 1H), 3.80 (s, 3H), 3.60 (d, J = 1.8 Hz, 2H), 1.57 (s, 3H). C
NMR (100 MHz, CDCl3): δ 159.6, 157.2, 155.8, 144.9, 142.9, 141.1, 129.6, 129.2, 127.9, 123.1,
120.3, 118.8, 118.3, 113.7, 112.9, 112.0, 60.3, 55.1, 47.2, 26.1. IR (neat): 2966.3, 2932.0,
2835.9, 1587.2, 1503.8, 1488.5, 1466.0, 1436.6 cm-1. HR MS (ESI+): calculated for
[C24H26NO2]+ 360.1964, found 360.1967.
2-(4-phenoxyphenyl)-N(-thiophen-2-ylmethyl)but-3-en-2-amine
(4i): yellow oil, 73% yield. 1H NMR (400 MHz, CDCl3): δ 7.46 (d,
J = 8.7 Hz, 2H), 7.34-7.30 (m, 3H), 7.09 (t, J = 7.4 Hz, 1H), 7.00
(d, J = 8.3 Hz, 2H), 6.97 (d, J = 8.7 Hz, 2H), 6.29 (dd, J = 1.9 Hz, J
= 2.9 Hz, 1H), 6.15 (d, J = 3.10 Hz, 1H), 6.06 (dd, J = 10.8 Hz, J = 17.4 Hz, 1H), 5.25 (dd, J =
6.4 Hz, 1H), 5.21 (s, 1H), 3.62 (s, 2H), 1.62 (s, 1H), 1.55 (s, 3H). 13C NMR (100 MHz, CDCl3):
δ 157.2, 155.8, 154.5, 144.3, 141.5, 140.5, 129.6, 127.9, 123.1, 118.8, 118.4, 113.2, 110.1, 106.1,
60.2, 40.4, 26.2. IR (neat): 2972.5, 2927.4, 1588.4, 1504.3, 1488.7 cm-1. HR MS (ESI+):
calculated for [C21H22NO2]+ 320.1651, found 320.1641.
2-(4-bromophenyl)-N-(2-methylbenzyl)but-3-en-2-amine
1
(5d): yellow oil, 79% yield. H NMR (400 MHz, CDCl3): δ
7.46-7.43 (m, 2H), 7.42-7.39 (m, 2H), 6.88 (d, J = 1.1 Hz, 1H),
6.78-6.72 (m, 2H), 6.03 (ddd, J = 1.4 Hz, J = 6.9 Hz, J = 14.1
Hz, 1H), 5.93 (s, 2H), 5.24 (s, 1H), 5.21 (dd, J = 1.1 Hz, J = 6.9 Hz, 1H), 3.49 (s, 2H), 1.53 (s,
3H), 1.41 (bs, 1H). 13C NMR (100 MHz, CDCl3): δ 147.6, 146.3, 145.4, 144.2, 135.0, 131.2,
128.4, 120.9, 120.5, 113.4, 108.7, 108.0, 100.8, 60.4, 47.0, 26.1. IR (neat): 2975.7, 2884.1,

ACCEPTED MANUSCRIPT
11
1634.9, 1501.6, 1480.1, 1440.9 cm-1. HR MS (ESI+): calculated for [C18H19BrNO2]+ 360.0599,
found 360.0598.
2-(2-(4-bromophenyl)but-3-3n-2-yl)-1,2,3,4-
1
tetrahydroisoquinoline (5g) yellow oil, 88% yield. H NMR (400
MHz, CDCl3): δ 7.47-7.41 (m, 4H), 7.12-7.07 (m, 3H), 7.00-6.98
(m, 1H), 6.05 (dd, J = 10.8 Hz, J = 17.6 Hz, 1H), 5.28 (dd, J = 1.0
Hz, J = 10.8 Hz, 1H), 5.23 (dd, J = 1.0 Hz, J = 17.6 Hz, 1H), 3.72 (d, J = 2.0 Hz, 2H), 2.87-2.72
13
(m, 3H), 2.61-2.54 (m, 1H), 1.51 (s, 3H). C NMR (100 MHz, CDCl3): δ 146.5, 142.1, 136.1,
135.2, 131.5, 128.9, 128.6, 126.9, 126.0, 125.6, 120.6, 114.9, 64.9, 49.4, 45.2, 30.5, 18.9. IR
(neat): 2979.1, 2918.7, 2806.9, 1634.8, 1585.8, 1481.5, 1453.0 cm-1. HR MS (ESI+): calculated
for [C19H21BrN]+ 342.0857, found 342.0874.
1-(2-(4-bromophenyl)but-3-3n-2-yl)-4-methylpiperidine
(5j)
1
yellow oil, 86% yield. H NMR (300 MHz, CDCl3): δ 7.40 (m, 4H),
5.96 (dd, J = 10.9 Hz, J = 17.6 Hz, 1H), 5.15-5.05 (m, 2H), 2.85
(ddd, J = 3.2 Hz, J = 5.8 Hz, J = 11.0 Hz, 1H), 2.65 (ddd, J = 3.2 Hz,
J = 5.8 Hz, J = 10.8 Hz, 1H), 2.14-1.93 (m, 3H), 1.60-1.52 (m, 2H), 1.39 (s, 3H), 1.29-1.13 (m,
2H), 0.9 (d, J = 6.2 Hz, 3H) . 13C NMR (100 MHz, CDCl3): δ 147.0, 143.8, 131.3, 128.6, 120.2,
113.5, 64.7, 47.6, 46.9, 35.6, 35.4, 31.6, 22.2, 17.9. IR (neat): 2947.8, 2916.9, 2868.6, 2801.0,
2841.6, 1635.0, 1586.7, 1485.5, 1454.9 cm-1. HR MS (ESI+): calculated for [C16H23BrN]+
308.1014, found 308.1004.
2-(2-(naphthalene-2-yl)but-3-en-2-yl)-1,2,3,4-
tetrahydroisoquinoline (6g): yellow oil, 73% yield. 1H NMR (400
MHz, CDCl3): δ 7.90 (s, 1H), 7.85-7.77 (m, 4H), 7.47-7.41 (m, 2H),
7.14-7.07 (m, 3H), 6.99-6.97 (m, 1H), 6.22 (dd, J = 10.9 Hz, J =
17.5 Hz, 1H), 5.32 (dd, J = 1.1 Hz, J = 4.0 Hz, 1H), 5.28 (dd, J = 1.2 Hz, J = 10.6 Hz, 1H), 3.78
13
(s, 2H), 2.87-2.76 (m, 3H), 2.65 (m, 1H), 1.64 (s, 3H). C NMR (100 MHz, CDCl3): δ 144.9,
142.6, 136.4, 135.4, 133.6, 132.6, 128.9, 128.3, 128.1, 127.6, 127.0, 126.0, 125.8, 125.6, 125.6,
125.0, 114.7, 65.2, 49.5, 45.3, 30.6, 18.7. IR (neat): 3058.2, 2978.5, 2917.9, 2804.5, 1630.8,

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1599.2, 1498.9, 1453.5, 1411.4 cm-1. HR MS (ESI+): calculated for [C23H24N]+ 314.1909, found
314.1921.
4-methyl-1-(2-(naphthalene-2-yl)but-3-en-2-yl)piperidine
(6j):
1
yellow solid, 84% yield, mp = 77-78 °C. H NMR (400 MHz,
CDCl3): δ 7.82-7.76 (m, 5H), 7.45-7.39 (m, 2H), 6.14 (dd, J = 10.9
Hz, J = 17.5 Hz, 1H), 5.18 (dd, J = 1.1 Hz, J = 4.4 Hz, 1H), 5.14
(dd, J = 1.1 Hz, J = 11.1 Hz, 1H), 2.93 (ddd, J = 3.1 Hz, J = 5.7 Hz, J = 10.9 Hz, 1H), 2.70 (ddd,
J = 3.2 Hz, J = 5.8 Hz, J = 10.7 Hz, 1H), 2.13 (dt, J = 2.3 Hz, J = 11.2 Hz, 1H), 2.03 (td, J = 2.3
Hz, J = 11.3 Hz, 1H), 1.60-1.56 (m, 1H), 1.53 (s, 3H), 1.34-1.18 (m, 4H), 0.91 (d, J = 6.2 Hz,
3H). 13C NMR (100 MHz, CDCl3): δ 145.5, 144.2, 133.5, 132.4, 128.2, 127.8, 127.5, 125.8,
125.6, 124.8, 113.4, 65.0, 47.7, 47.0, 35.7, 35.5, 31.7, 22.2, 17.9. IR (neat): 3057.9, 2947.9,
2912.9, 2866.5, 2840.6, 2801.6, 1632.0, 1598.8, 1503.5, 1455.2, 1441.9, 1410.4 cm-1. HR MS
(ESI+): calculated for [C20H26N]+ 280.2065, found 280.2066.
N-(2-methylbenzyl)1-vinyl-1,2,3,4-tetrahydronaphthalen-1-amine
(7b) yellow oil, 78% yield. 1H NMR (400 MHz, CDCl3): δ 7.42 (dd, J =
HN
Me
1.6 Hz, J = 7.6 Hz, 1H), 7.33-7.31 (m, 1H), 7.20-7.09 (m, 6H), 6.04 (dd,
J = 10.6 Hz, J = 17.3 Hz, 1H), 5.11 (dd, J = 1.4 Hz, J = 10.6 Hz, 1H),
4.92 (dd, J = 1.4 Hz, J = 17.4 Hz, 1H), 3.63 (d, J = 12.3 Hz, 1H), 3.44 (d,
J = 12.3 Hz, 1H), 2.88-2.74 (m, 2H), 2.31 (s, 3H), 2.20-2.14 (m, 1H), 1.94-1.82(m, 3H), 1.50 (bs,
1H). 13C NMR (100 MHz, CDCl3): δ 146.2, 139.8, 139.3, 138.4, 136.7, 130.3, 129.2, 128.9,
128.5, 127.0, 126.7, 126.1, 125.9, 114.2, 60.6, 44.7, 33.2, 30.3, 19.9, 19.2. IR (neat): 3060.24,
3016.3, 2931.8, 2863.4, 1634.3, 1603.6, 1486.4, 1445.1 cm-1. HR MS (ESI+): calculated for
[C20H24N]+ 278.1909, found 278.1898.
2-(1-vinyl-1,2,3,4-tetrahydronaphthalen-1-yl)-1,2,3,4-
tetrahydroisoquinoline (7g): yellow oil, 89% yield. 1H NMR (400 MHz,
CDCl3): δ 7.70 (dd, J = 1.8 Hz, J = 7.5 Hz, 1H), 7.17-7.04 (m, 5H), 6.96-
6.94 (m, 1H), 6.03 (ddd, J = 0.7 Hz, J = 10.9 Hz, J = 17.5 Hz, 1H), 5.16
(dd, J = 1.1 Hz, J = 3.8 Hz, 1H), 5.12 (dd, J = 1.1 Hz, J = 10.4 Hz, 1H), 3.86 (d, J = 14.7 Hz,
1H), 3.58 (d, J = 14.7 Hz, 1H), 2.82-2.73 (m, 4H), 2.64-2.58 (m, 1H), 2.15-2.10 (m, 1H), 2.04-

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1.92 (m, 2H), 1.91-1.80 (m, 2H). 13C NMR (100 MHz, CDCl3): δ 145.1, 140.6, 138.3, 136.6,
135.5, 129.0, 128.9, 126.9, 126.47, 126.43, 125.9, 125.5, 113.7, 64.3, 49.2, 44.7, 30.6, 30.5, 23.7,
21.0. IR (neat): 3060.5, 3016.2, 2931.8, 2865.3, 2801.5, 2741.9, 1633.8, 1484.9, 1447.4 cm-1.
HR MS (ESI+): calculated for [C21H24N]+ 290.1909, found 290.1906.
N-(2-methylbenzyl)-2-(thiophen-2-yl)but-3-en-2-amine (8b) yellow
1
oil, 74% yield. H NMR (400 MHz, CDCl3): δ 7.35-7.33 (m, 1H), 7.21
(dd, J = 1.3 Hz, J = 4.8 Hz, 1H), 7.17-7.12 (m, 3H), 6.96-6.94 (m, 2H),
6.15 (dd, J = 10.6 Hz, J = 17.3 Hz, 1H), 5.28 (d, J = 17.4 Hz, 1H), 5.20
(d, J = 10.6 Hz, 1H), 3.64 (s, 2H), 2.33 (s, 3H), 1.68 (s, 3H), 1.51 (bs, 1H). 13C NMR (75 MHz,
CDCl3): δ 152.9, 144.6, 138.9, 136.8, 130.3, 128.9, 127.1, 126.6, 126.1, 124.4, 123.8, 113.4,
59.6, 45.2, 27.1, 19.2. IR (neat): 3068.3, 3016.7, 2970.5, 2924.0, 2851.3, 1635.43, 1490.0,
1460.63, 1408.7 cm-1. HR MS (ESI+): calculated for [C16H20NS]+ 258.1316, found 258.1310.
N-benzyl-4-(tert-butyl)-1-vinylcyclohexanamine (9a): 69% combined yields, 2.8:1
tBu
1
dr. 9a-major isomer: colourless oil, 51% yield. H NMR (400 MHz, CDCl3): δ
7.37-7.36 (m, 2H), 7.33-7.29 (m, 2H), 7.25-7.21 (m, 1H), 5.79 (dd, J = 10.8 Hz, J =
NH
17.6 Hz, 1H), 5.09 (d, J = 9.9 Hz, J = 1.5 Hz, 1H), 5.06 (dd, J = 1.5 Hz, J = 3.1 Hz,
Ph
1H), 3.54 (s, 2H), 1.81-1.79 (m, 2H), 1.58-1.56 (m, 2H), 1.41-1.35 (m, 4H), 1.23
13
(bs, 1H), 1.03-0.95 (m, 1H), 0.87 (s, 9H). C NMR (75 MHz, CDCl3): 146.93, 141.82, 128.28,
128.19, 126.64, 111.69, 55.21, 47.77, 46.24, 34.80, 32.47, 27.59, 21.91. IR (neat): 2930.2,
2863.0, 1635.0, 1495.4, 1452.7, 1412.1, 1393.1, 1364.9 cm-1. HR MS (ESI+): calculated for
[C19H30N]+ 272.2372, found 272.2363.
9a-minor isomer: colourless oil, 18% yield. 1H NMR (400 MHz, CDCl3): δ 7.32-7.29 (m, 3H),
7.27-7.26 (m, 1H), 7.23-7.19 (m, 1H), 5.60 (dd, J = 10.9 Hz, J = 17.8 Hz, 1H), 5.33 (dd, J = 10.9
Hz, J = 1.4 Hz, 1H), 5.15 (dd, J = 1.4 Hz, J = 17.8 Hz, 1H), 3.43 (s, 2H), 1.98-1.94 (m, 2H),
1.65-1.62 (m, 2H), 1.54 (bs, 1H), 1.45-1.38 (m, 2H), 1.14 (m, 2H), 1.06-0.99 (m, 1H), 0.83 (s,
9H). 13C NMR (100 MHz, CDCl3): 142.1, 128.3, 128.1, 126.7, 115.4, 56.9, 48.2, 46.3, 36.9,
32.3, 27.6, 27.5, 23.8. IR (neat): 2930.5, 2853.9, 1670.4, 1495.1, 1453.3, 1408.1, 1393.4, 1365.1
cm-1. HR MS (ESI+): calculated for [C19H30N]+ 272.2372, found 272.2379.

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1.3
NMR Spectra
4-II
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3c
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