FeCl3-catalyzed addition of nitrogen and 1,3-dicarbonyl nucleophiles to olefins

Article abstract of DOI:10.1016/j.jorganchem.2010.09.031

A direct intermolecular addition of nitrogen and 1,3-dicarbonyl nucleophiles to stabilized double bonds (styrenes, 1,3-dienes, enol-ethers, sugars.) in the presence of green and inexpensive FeCl₃ catalyst is described.

Full text of DOI:10.1016/j.jorganchem.2010.09.031

Journal of Organometallic Chemistry 696 (2011) 296e304
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
FeCl3-catalyzed addition of nitrogen and 1,3-dicarbonyl nucleophiles to olefins
Christophe Dal Zotto a, Julien Michaux a, Araceli Zarate-Ruiz a, Eric Gayon a, David Virieux a,
,
b
b
b
b,
*
Jean-Marc Campagne a , Vincent Terrasson , Grégory Pieters , Anne Gaucher , Damien Prim
*
a Institut Charles Gerhardt, UMR 5253 CNRS-UM2-UM1-ENSCM, 8 Rue de l’Ecole Normale, 34296 Montpellier, France
b Institut Lavoisier UMR CNRS 8180, Université de Versailles-Saint-Quentin-en-Yvelines, 45, Avenue des Etats-Unis, F-78035 Versailles, France
a r t i c l e i n f o
a b s t r a c t
Article history:
A direct intermolecular addition of nitrogen and 1,3-dicarbonyl nucleophiles to stabilized double bonds
(styrenes, 1,3-dienes, enol-ethers, sugars..) in the presence of green and inexpensive FeCl3 catalyst is
described.
Received 21 July 2010
Received in revised form
9 September 2010
Accepted 14 September 2010
Available online 8 October 2010
Ó 2010 Elsevier B.V. All rights reserved.
Keywords:
Iron
Hydroamination
Atom economy
1. Introduction
we were puzzled if these products could arise from the hydro-
amination of styrenes. In a preliminary report [4], we reported the
The addition of Carbon, Nitrogen and Oxygen nucleophiles to
CeC double bond is desirable in terms of atom economy to create
new CeC, CeN and CeO bonds. These reactions should produce no
stoichiometric by-products and meet the increasing demand for
environment benign organic synthesis processes. Moreover, if such
transformations could be catalyzed by non-toxic, abundant and
inexpensive catalysts such as iron complexes [1,2], it could be very
close to the definition of an ideal ‘green’ reaction [3]. We would like
to report in this article a full account on our recent work on iron-
catalyzed addition of nitrogen and 1,3-dicarbonyl nucleophiles to
stabilized double bonds (styrenes, 1,3-dienes, enol-ethers, sugars..)
(Scheme 1) [4].
preparation of the formation of the CeN bond at benzylic positions
through iron-catalyzed intermolecular hydroamination of styrenes
[6,7]. In order to set the best catalytic combination, several iron
sources under different set of reaction conditions have been
explored. Initial experiments were conducted with styrene and
TsNH2 in order to prepare hydroaminated product 1 (Scheme 2).
Among the tested iron sources such as FeCl2, FeS, Fe(NO3)3, Fe
(acac)3, FeBr3, FeCl3 on silica and anhydrous FeCl3, best results were
obtained in the presence of 10% of FeCl3$6H2O in dioxane at 120 ꢀC
leading to the hydroaminated product 1 in 73% yield.
The use of other nitrogen sources was next tested in the hydro-
amination of styrene (Table 1). Whereas electron-poor nitrogen
nucleophiles, such as p-NO2-aniline (entry 2), 2-NO2-4-toluidine
(entry 3), or p-NO2-benzamide (entry 4), gave encouraging results,
no reaction could be observed with more basic nitrogen nucleo-
philes such as phtalimide or 2,4-DNPH. The use of TMSN3, which
proved to be a good pro-nucleophile in the substitution of benzylic
alcohols [5a], was also investigated. The formation of the benzylic
CeN3 bond was clearly evidenced in the crude material through 1H
and 13C NMR analyses and a 60% conversionwas estimated (entry 5).
However, owing to product instability (degradation upon purifica-
tion by column chromatography) a very low yield (12%) was
obtained. Despite considerable experiments and careful purification
attempts, the yield could not be improved. Scope and limitations
were next tested by varying the nature of the vinyl arene residue
(Table 1, entries 7e16). Electron-donating groups are well tolerated
2. Results and discussion
2.1. Hydroamination reactions
As part of a program directed towards the preparation of new
mono- and diamines and their use as ligands in the design of new
transition metal complexes, we became interested in the prepara-
tion of benzylic amines. Such targets can be efficiently obtained
through gold-promoted amination of benzylic alcohols [5b], and
* Corresponding authors.
E-mail addresses: jean-marc.campagne@enscm.fr (J.-M. Campagne), prim@
chimie.uvsq.fr (D. Prim).
0022-328X/$ e see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.09.031

C.D. Zotto et al. / Journal of Organometallic Chemistry 696 (2011) 296e304
297
(TsNH2, nitro-anilines, carboxamides.). The use of alternatives
nucleophiles was then questioned [8].
Nu
Nu-H
H
ED
ED
FeCl3•6H2O 10 mol%
Solvent
2.2. Addition of 1,3-dicarbonyl compounds
We thus turned our attention to the use of carbon nucleophiles,
such as as 1,3-dicarbonyl derivatives. We first examine a model
reaction of styrene with acetylacetone (Table 2). After a short
optimization dealing with catalyst amount (entries 1e3), iron
sources (entries 4e7), equivalent of nucleophiles (compare entries
3 and 8e9), solvents (entries 9e14), temperature (entries 15e16)
and reaction time (entries 17e18), the following conditions found
to be optimal in our hands: a 10-fold excess of acetylacetone in DCE
at 100 ꢀC for 20 hours allows the formation of 25 in 86% yield.
Consequently, other nucleophiles and substrates were exam-
ined and FeCl3 was able to promote a clean addition of 1,3-diphen
ylpropane-1,3-dione or ethyl acetoacetate to styrene, and p-Me-
styrene to give compounds 26, 27 and 28 in 62, 79 and 58% yields
respectively (Scheme 6) [10].
However, at the time we got these preliminary results [9], Beller
[10] described very similar results (compounds 25, 26, 27 and 28
have been isolated in 82, 69, 76% and 64% yields respectively) and
extended the scope to other various nucleophiles and styrenes,
including a very nice synthesis of warfarin. In the light of these
results, we thus turned our attention to the use of other electro-
philes such as dienes and enol-ethers, not developped in the Bel-
ler’s publication [10,11].
Starting from 1,3-cyclohexadiene (Scheme 7), various 1,3-dicar
bonyl derivatives were successfully introduced as illustrated in
compounds 29, 30 and 31 isolated in 64, 40 (44/56 dr), and 48%
yields respectively [11c,12,13]. More surprisingly, the use of cyclic
derivatives such as 2-acetylcyclopentanone and dimedone led to
more disappointing results (Scheme 7, compounds 32 [14] and 33).
From cyclic enol-ethers (Scheme 8), such as dihydropyran (and
dihydrofuran)and acetylacetone(or1,3-diphenylpropane-1,3-dione),
compounds 34 [11a], 35 [11a] and 36 [11c] were isolated in 54, 58 and
30% yields respectively.
Scheme 1.
in these reactions (7e11) whereas electron-withdrawing groups
completely inhibit the hydroamination reaction (see compounds 12
and 13). Noteworthy, paradoxical halogens (ꢁI, þM) substituents in
the paraposition, lead tothe hydroaminated products 10e11 in good
yields, 69 and 63% yields respectively.
Interestingly, in the presence of strong electron-donating
groups such as p-Me or 2,4-diMe, the reactions could be carried out
at room temperature, in moderate to good yields (7e9). The
hydroamination is also quite sensitive to steric hindrance: reactions
of either
a- or b-substituted styrenes were rather slow and the
hydroaminated products isolated in low yields (14e16). It is also
worthnoting that styrene polymerization and/or hydroarylation
by-products could be observed in the crude NMR spectra when
hydroamination reluctant substrates were used.
Finally, the hydroamination of 1-(chloromethyl)-4-vinyl-
benzene 17, commercialy available as a mixture of 1-(chlor-
omethyl)-4-vinylbenzene and 1-(chloromethyl)-3-vinylbenzene,
was carried out and led to a mixture of monoaminated (at the
benzylic position) 18 and diaminated 19 compounds in 15 and 43%
yields respectively (Scheme 3).
According to the scope of the reaction, electron-donating groups
on the aromatic ring accelerate the reaction, whereas electron-
withdrawing groups inhibit the hydroamination. Thus a mecha-
nism (Schemes 4) involving a transient carbocation or a polarized
p
-complexed double bond can be envisioned, in which a stabiliza-
tion of a carbocation or a
key-step.
d
þ charge intermediate is involved in the
The use of alternative stabilizating groups, such as 1,3-dienes,
enol-ethers or glycals was thus examined (Scheme 5). Indeed,
starting from1,3-cyclohexadiene in the presence of TsNH2 (5 equiv.),
the hydroamination product 20 was isolated in 56% yield [7l].
Dihydropyran was next engaged in hydroamination reactions in the
presence of TsNH2 and p-NO2-aniline and gratifyingly compounds
21 and 22 were isolated in 89 and 54% yield, respectively. Usually an
excess (5 equiv) of nitrogen nucleophile is necessary to get a full
conversion, however in the latter case, 22 and p-nitroaniline could
not be separated by flash chromatography and thus, dihydropyran
was used in excess (3 equiv) and slowly added over 4 hours, through
a syringe pump, at 80 ꢀC to give 22 in 54% yield. Finally, moving to
glycals, such as 23, the hydroamination reactions proved to be more
reluctant and amongmanyother unidentifedproducts, amino-sugar
24, resulting from the expected hydroamination reaction but also
from the nucleophilic substitution on the primary acetate, could be
identified in less than 20% yield.
Moving to glucal 23, the reaction led to the degradation of the
starting glucal and the generation of many by-products where 37
could not be identifed regardless of the nature of the protecting
group (R ¼ Ac or Bn). Consequently, we thus turned our attention to
sugars [14] and in the case of 2,3,4-tri-O-benzyl-
b-D-arabinofur-
anose 38, gratifyingly, C-glucoside 39 was isolated in 54% yield and
7:3 dr (Scheme 9).
In this reaction, a slow addition of 38 is required to prevent the
formation of the dimeric sugar by-product 40 which could be
obtained in 28% yield using FeCl3 at 50 ꢀC, and in 43% yield using
NaAuCl4 at room temperature (Scheme 10).
3. Conclusion
In conclusion, we have demonstrated that Iron(III) chloride is
able to catalyze the addition of nitrogen and 1,3-dicarbonyl
nucleophiles to double bonds such as vinyl arenes, enol-ethers and
1,3-dienes. The attractiveness of these reactions lies on their atom
economy and the use of environmentally begin and cheap Iron(III)
chloride in the absence of any additive or ligand.
In summary, the hydroamination of double bonds bearing
electron-donating groups, such as styrenes, 1,3-dienes or enol-
ethers can be carried out in dioxane (or DCE) in the presence of
a catalytic amount of FeCl3 and electron-poor nitrogen nucleophiles
4. Experimental
NHTs
FeCl3•6H2O 10 mol%
dioxane, 120 °C
+ TsNH2
4.1. General procedure for the hydroamination of styrenes
and 1,3-dienes
1
73%
To a stirred solution of TsNH2 (5 mmol) and FeCl3 (0.1 mmol) in
dioxane (or DCE, 5 mL) was added vinyl arene (1 mmol) and the
Scheme 2.

298
C.D. Zotto et al. / Journal of Organometallic Chemistry 696 (2011) 296e304
Table 1
Hydroamination of stryrene derivatives: scope and limitations.
Entry
Vinyl-arene
Nitrogen nucleophile
Conditions
A
Product
Nꢀ
Yield (%)
73
1
TsNH2
1
2
3
4
5
6
7
8
9
p-NO2-aniline
p-Me, o-NO2-aniline
p-NO2-benzamide
TMSN3
B
B
B
A
A
C
C
C
2
3
4
5
6
7
8
9
70
41
30
12
59
53
57
43
PhSO2NH2
TsNH2
4-Me-2-NO2-aniline
8
p-NO2-aniline
10
11
12
TsNH2
TsNH2
TsNH2
A
A
A
10
11
12
69
63
5

C.D. Zotto et al. / Journal of Organometallic Chemistry 696 (2011) 296e304
299
Table 1 (continued )
Entry
Vinyl-arene
Nitrogen nucleophile
TsNH2
Conditions
A
Product
Nꢀ
Yield (%)
13
14
13
e
p-NO2-aniline
A
14
12
15
16
TsNH2
TsNH2
A
A
15
16
11
e
Conditions: A: dioxane reflux. B: DCE-reflux. C: Dioxane r.t.
yellow solution was refluxed for 20 h (bath temperature: 120 ꢀC).
After cooling to RT and usual work-up, the residue was purified on
silica gel to afford the hydroaminated compound.
1H NMR (300 MHz, CDCl3):
d
(ppm) 1.56 (d, J ¼ 6.8 Hz, 3H), 2.14
(s, 3H), 4.60 (quintet, J ¼ 6.7 Hz, 1H), 6.47 (d, J ¼ 8.9 Hz, 1H), 7.01
(dd, J ¼ 8.9 and 1.9 Hz, 1H), 7.18e7.20 (m, 2H), 7.25e7e28 (m, 3H),
7.90 (d, J ¼ 1.0 Hz, 1H), 8.25 (broad s, 1H).
4.1.1. N-(1-phenylethyl)-4-methylbenzenesulfonamide (1)
According to the general procedure, compound 1 was purified
on silica gel (AcOEt/Heptane 3/7).
13C NMR (75 MHz, CDCl3):
d (ppm) 19.9, 25.1, 53.1, 115.1, 125.1,
125.6, 125.9, 127.3, 128.9, 131.7, 137.5, 142.7, 143.8.
MS (CI, NH3) m/z (%): 257 (M þ Hþ, 35), 256 (M. þ, 10), 213 (10),
197 (100).
73% yield, white solid, mp 78e79 ꢀC.
1H NMR (300 MHz, CDCl3):
d
(ppm) 1.43 (d, J ¼ 6.9 Hz, 3H), 2.39
(s, 3H), 4.47 (quintet, J ¼ 6.8 Hz, 1H), 5.00 (broad d, J ¼ 6.9 Hz, 1H),
7.09e7.14 (m, 2H), 7.16e7.21 (m, 5H), 7.60 (d, J ¼ 8.3 Hz, 2H).
4.1.4. 4-nitro-N-(1-phenylethyl)benzamide (4)
According to the general procedure, compound 4 was purified
on silica gel (AcOEt/PE 5/95).
13C NMR (75 MHz, CDCl3):
d (ppm) 21.6, 23.6, 53.7, 126.2, 127.2,
127.5, 128.6, 129.5, 137.8, 142.2, 143.2.
30% yield, yellowish solid.
Data are in accordance with previously reported data [5b].
1H NMR (300 MHz, CDCl3):
d
(ppm) 1.57 (d, J ¼ 6.8 Hz, 3H), 5.25
(q, J ¼ 6.8 Hz, 1H), 7.07 (d, J ¼ 6.7 Hz, 1H), 7.21e7.35 (m, 5H), 8.01 (d,
4.1.2. N-(1-phenylethyl)-4-nitroaniline (2)
J ¼ 9.1 Hz, 2H), 8.23 (d, J ¼ 9.1 Hz, 2H).
According to the general procedure, compound 2 was purified
Data are in accordance with previously reported data [7e].
on silica gel (AcOEt/PE 2/8) 70% yield, yellow solid, mp 81e82 ꢀC.
1H NMR (300 MHz, CDCl3):
d
(ppm) 1.51 (d, J ¼ 6.9 Hz, 3H), 4.51
4.1.5. N-(1-phenylethyl)-benzenesulfonamide (6)
According to the general procedure, compound 6 was purified
on silica gel (AcOEt/PE 2/8).
(q, J ¼ 6.8 Hz, 1H), 4.82 (broad s, 1H), 6.38 (d, J ¼ 9.1 Hz, 2H),
7.18e7.27 (m, 5H), 7.92 (d, J ¼ 9.2 Hz, H).
13C NMR (75 MHz, CDCl3)
d
(ppm) 24.5, 53.3, 111.8, 125.6, 126.2,
59 % yield, white solid.
127.5,128.9, 138.1, 143.2, 152.2.
1H NMR (300 MHz, CDCl3):
(quint, J ¼ 6.8 Hz,1H), 5.04 (d, J ¼ 6.8 Hz,1H), 7.09 (m, 2H), 7.16 (m, 3H),
7.38 (d, J ¼ 8.3 Hz, 1H), 7.50 (t, J ¼ 8.3 Hz, 2H), 7.72 (d, J ¼ 8.3 Hz, 2H).
d
(ppm) 1.43 (d, J ¼ 6.8 Hz, 3H), 4.49
MS (CI, NH3) m/z (%) 502 (2M þ NHþ4 , 10), 485 (2M þ Hþ, 45), 260
(M þ NHþ4 , 55), 243 (M þ Hþ, 100), 242 (M. þ, 45), 227 (10).
Data are in accordance with previously reported data [15].
NHTs
R
4.1.3. N-(1-phenylethyl)-4-methyl-2-nitroaniline (3)
According to the general procedure, compound 2 was purified
on silica gel (AcOEt/PE 5/95).
[FeIII]
R
41% yield, orange solid, mp 87e88 ꢀC.
[FeIII]
[Fe]
δ+
Ts-NH2
δ-
R
(pNO2Ph)NH
NH2
or
FeCl3•6H2O 10%
+
+
Cl
(pNO2Ph)NH
19 (43%)
DCE, 80 °C
(pNO2Ph)NH
18 (15%)
R
17
NO2
Scheme 3. Mono vs. diamination reactions.
Scheme 4. Postulated mechanism.

300
C.D. Zotto et al. / Journal of Organometallic Chemistry 696 (2011) 296e304
O
O
NHTs
TsNH2
FeCl3•6H2O 10mol%
FeCl3•6H2O 10mol%
DCE, 80 °C
R2
R1
R2
R1
+
20
dioxane, 80 °C
O
O
56% yield
NHTs
21
R
TsNH2
O
O
O
O
O
O
R
O
O
O
O
FeCl3•6H2O 10mol%
OEt
Ph
Ph
dioxane, 80 °C
89% yield
NH(p-NO2Ph)
p-NO2Aniline
O
O
28
58%
27
79%
25
26
FeCl3•6H2O 10mol%
86%
62%
49:51 dr
dioxane, 80 °C
22
54% yield
Slow addition
Scheme 6.
OAc
OAc
TsNH2
chromatography (silica gel, EtOAc/PE 2/8) yielded 8 in 57% as an
AcO
FeCl3•6H2O 10mol%
AcO
AcO
orange solid.
1H NMR (300 MHz, CDCl3):
d
(ppm) 1.50 (d, J ¼ 6.6 Hz, 3H), 2.13
dioxane, 80 °C
O
NHTs
(s, 3H), 2.21 (s, 3H), 2.34 (s, 3H), 4.73 (quint, J ¼ 6.6 Hz, 1H), 6.31 (d,
J ¼ 8.4 Hz, 1H), 6.86e6.93 (m, 2H), 7.00 (dd, J ¼ 2.1, 8.9 Hz, 1H), 7.10
(d, J ¼ 8.4 Hz, 1H), 7.89 (s, 1H), 8.24 (br s, 1H).
O
23
TsHN
24 ( < 20% yield)
13C NMR (75 MHz, CDCl3):
d (ppm) 18.8, 19.9, 20.9, 23.1, 49.5,
Scheme 5. Diene and enol-ether hydroaminations.
114.8,124.5,124.9,125.9,127.5,127.6,131.6,134.0,136.7,137.6,138.5,
142.7.
Data are in accordance with previously reported data [16].
MS (CI, NH3): m/z (%) 285 (M þ NHþ4 , 100), 284 (M þ Hþ), 50, 150
(25), 133(95).
4.1.6. N-(1-p-tolylethyl)-tosylamide (7)
According to the general procedure for hydroamination, the
reaction was carried out at rt in dioxan. Purification by flash column
chromatography (silica gel, EtOAc/heptane 2/8) yielded 7 in 53% as
a white solid. M.p. 114e115 ꢀC (Lit.7c 116e118 ꢀC)
4.1.8. N-[1-(2,4-dimethylphenyl)ethyl]-4-nitroaniline (9)
According to the general procedure for hydroamination, the
reaction was carried out at rt in dioxan. Purification by flash column
chromatography (silica gel, EtOAc/PE 2/8) yielded 9 in 43% as
a yellow solid. Mp: 114e115 ꢀC.
1H NMR (CDCl3, 500 MHz):
d
(ppm) 1.42 (d, J ¼ 6.8 Hz, 3H), 2.29
(s, 3H), 2.41 (s, H), 4.43 (quint, J ¼ 6.8 Hz, 1H), 4.89 (d, J ¼ 6.8 Hz,
1H NMR (300 MHz, CDCl3):
d
(ppm) 1.55 (d, J ¼ 6.2 Hz, 3H), 2.32
1H), 7.01 (m, 4H), 7.20 (d, J ¼ 8.1 Hz, 2H), 7.64 (d, J ¼ 8.1 Hz, 2H).
(s, 3H), 2.43 (s, 3H), 4.76 (quint, J ¼ 6.2 Hz, 1H), 5.07 (d, J ¼ 6.2 Hz,
1H), 6.42 (d, J ¼ 9.2 Hz, 2H), 6.97e7.05 (m, 2H), 7.22 (d, J ¼ 7.7 Hz,
1H), 8.01 (d, J ¼ 9.2 Hz, 2H).
13C NMR (CDCl3, 75 MHz):
d (ppm) 21.0, 21.5, 23.6, 53.5, 126.1
(2C), 127.2 (2C), 129.2 (2C), 129.4 (2C), 137.1, 137.8, 139.3, 143.0.
Data are in accordance with previously reported data [7e].
13C NMR (75 MHz, CDCl3):
d (ppm) 18.9, 20.9, 22.5, 49.5, 111.5,
124.3, 126.3, 127.4, 131.7, 134.4, 137.0, 137.8, 138.0, 152.2.
4.1.7. N-[1-(2,4-dimethylphenyl)ethyl]-4-methyl-2-nitroaniline (8)
According to the general procedure for hydroamination, the
reaction was carried out at rt in dioxan. Purification by flash column
MS (CI, NH3): m/z (%) 541 (2M þ NHþ4 , 100), 420 (10), 403 (25),
288 (M þ NHþ4 , 10), 271 (M þ Hþ, 30), 270 (25), 255 (10), 133 (30).
4.1.9. N-(1-(4-bromophenyl)ethyl)-tosylamide (10)
According to the general procedure for hydroamination, the
reaction was carried out in dioxan. Purification by flash column
chromatography (silica gel, EtOAc/heptane 2/8) yielded 10 in 63%
yield as a white solid. Mp: 139e140 ꢀC
Table-2
Iron(III) catalyzed addition of acetylacetone to styrene.
Entry Catalyst (mol%)
Acetyl
acetone
(equiv.)
Conditions
Isolated
yield (%)
1H NMR (CDCl3, 300 MHz):
d
(ppm) 1.37 (d, J ¼ 6.9 Hz, 3H), 2.41
(s, 3H), 4.42 (quint, J ¼ 6.9 Hz, 1H), 5.48 (d, J ¼ 7.0 Hz), 7.00 (d,
1
2
3
4
5
6
7
8
FeCl3 (100%)
FeCl3 (20%)
FeCl3 (10%)
FeCl2 (10%)
Fe(acac)3 (10%)
FeCl3$6H2O (10 mol%)
2.5
2.5
2.5
2.5
2.5
2.5
Dioxane, 120 ꢀC, 20 h 70
Dioxane, 120 ꢀC, 20 h 55
Dioxane, 120 ꢀC, 20 h 51
Dioxane, 120 ꢀC, 20 h NR
Dioxane, 120 ꢀC, 20 h 26
Dioxane, 120 ꢀC, 20 h 43
Dioxane, 120 ꢀC, 20 h 54
Dioxane, 120 ꢀC, 20 h 71
Dioxane, 120 ꢀC, 20 h 77
O
O
R2
R1
FeCl3$6H2O (10 mol%)a 2.5
FeCl3•6H2O 10mol%
DCE, 80 °C
R2
R1
+
FeCl3$6H2O (10 mol%)a
5
O
O
9
FeCl3$6H2O (10 mol%)a 10
FeCl3$6H2O (10 mol%)a 10
FeCl3$6H2O (10 mol%)a 10
FeCl3$6H2O (10 mol%)a 10
FeCl3$6H2O (10 mol%)a 10
FeCl3$6H2O (10 mol%)a w100
FeCl3$6H2O (10 mol%)a 10
FeCl3$6H2O (10 mol%)a 10
FeCl3$6H2O (10 mol%)a 10
FeCl3$6H2O (10 mol%)a 10
10
11
12
13
14
15
16
17
18
Toluene, 120 ꢀC, 20 h
THF, 60 ꢀC, 20 h
DCM, 60 ꢀC, 20 h
DCE, 80 ꢀC, 20 h
Neat, 120 ꢀC, 20 h
DCE, 100 ꢀC, 20 h
DCE, 120 ꢀC,b 20 h
DCE, 80 ꢀC, 8 h
8
NR
11
86
11
86
81
54
79
O
O
O
O
O
O
Ph
O
O
O
OEt
O
Ph
33
29
32
14%
31
30
40%
NR
DCE, 60 ꢀC, 36 h
64%
48%
(29% in dioxane)
a
FeCl3$6H2O (10 mol%) is finely ground before utilization.
Reaction carried out on a Wheaton vial.
b
Scheme 7.

C.D. Zotto et al. / Journal of Organometallic Chemistry 696 (2011) 296e304
301
R2
O
BnO
FeCl3•6H2O 10 mol%
DCE, 50°C
O
FeCl3•6H2O 10mol%
DCE, 80 °C
R2
R1
Ph
O
BnO
BnO
+
O
O
O
OBn
OBn
28% yield
O
OH
O
O
R
R1
O
O
or
NaAuCl4•2H2O 10 mol%
DCM, rt
BnO
BnO
O
OBn
R
O
O
38
OR
40
43% yield
O
O
O
OBn
O
O
O
O
Scheme 10.
Ph
O
RO
34
54%
35
36
OR
37 (R=OAc, Bn)
NR
58%
30%
(at 60 °C)
13C NMR (75 MHz, CDCl3):
d (ppm) 30.4, 56.5, 113.4, 125.2, 125.7,
127.0, 128.9, 137.8, 145.3, 151.5. MS (CI, NH3) m/z (%) 513 (2M þ NHþ4 ,
85), 392 (10), 274 (M þ NH4þ, 30), 257 (M þ Hþ, 100), 256 (M.þ, 40),
119 (10).
Scheme 8.
Data are in accordance with previously reported data [17].
J ¼ 8.4 Hz, 2H), 7.17 (d, J ¼ 8.1 Hz, 2H), 7.27 (d, J ¼ 8.4 Hz, 2H), 7.58
(d, J ¼ 8.1 Hz, 2H)
4.1.13. N-(1-phenylpropyl)-tosylamide (15)
13C NMR (CDCl3, 75 MHz):
d (ppm) 21.5, 23.4, 53.2, 121.2 (2C),
According to the general procedure for hydroamination, the
reaction was carried out in dioxan. Purification by flash column
chromatography (silica gel, EtOAc/heptane 3/7) yielded 15 in 11%
yield as a white solid. Mp: 102e103 ꢀC (Lit.19 108e109 ꢀC)
127.1, 128.1 (2C), 129.5 (2C), 131.5 (2C), 137.5, 141.2, 143.4.
IR:
n
(cmꢁ1) 3239, 2971, 1596, 1488, 1438, 1321, 1153
79
HRMS (ESI): m/z [M þ Na]þ 376.0009, calc. for C15
H BrNNaO2S:
16
81
375.9983; 377.9999, calc. for C15
H BrNNaO2S: 377.9962.
16
1H NMR (CDCl3, 500 MHz):
d
(ppm) 0.79 (t, J ¼ 7.4 Hz, 3H), 1.74
(m, 2H), 2.36 (s, 3H), 4.20 (q, J ¼ 7.4 Hz, 1H), 5.23 (d, J ¼ 7.4 Hz, 1H),
7.02 (m, 2H), 7.11 (d, J ¼ 8.1 Hz, 2H), 7.15 (m, 3H), 7.56 (d, J ¼ 8.2 Hz,
2H).
4.1.10. N-(1-(4-fluorophenyl)ethyl)-tosylamide (11)
According to the general procedure for hydroamination, the
reaction was carried out in dioxan. Purification by flash column
chromatography (silica gel, EtOAc/heptane 2/8) yielded 11 in 63%
yield as a white solid. Mp: 115e116 ꢀC (Lit.7f 118e119 ꢀC)
13C NMR (CDCl3, 75 MHz):
d (ppm) 10.6, 21.5, 30.7, 59.9, 126.7
(2C), 127.1 (2C), 127.3, 128.4 (2C), 129.3 (2C), 137.8, 140.8, 143.0.
Data are in accordance with previously reported data [18].
1H NMR (CDCl3, 300 MHz):
d
(ppm) 1.47 (d, J ¼ 6.9 Hz, 3H), 2.38
4.1.14. N-(vinylbenzyl)-4-nitroaniline (18) N,N0-di-4-nitrophenyl-
1-(aminomethylphenyl)-ethylamine (19)
(s, 3H), 4.45 (quint, J ¼ 7.0 Hz, 1H), 5.76 (d, J ¼ 7.3 Hz, 1H), 6.83 (wt,
J ¼ 8.7 Hz, 2H), 7.08 (m, 2H), 7.16 (d, J ¼ 8.0 Hz, 2H), 7.62 (d,
J ¼ 8.3 Hz, 2H).
According to the general procedure for hydroamination, the
reaction was carried out in refluxing DCE. Separation by flash
column chromatography (silica gel, EtOAc/PE 2/8 then 2/3) yielded
18 in 15% as a yellow solid and 19 in 43% as a yellow oil.
18 (description of the meta substituted product obtained as the
13C NMR (CDCl3, 75 MHz):
d (ppm) 21.4, 23.6, 53.0, 115.2 (d, J
¼ 21.6 Hz, 2C), 127.1 (2C), 127.9 (d, J ¼ 8.4 Hz, 2C), 129.4 (2C), 137.6,
138.1, 143.2, 161.9 (d, J ¼ 245.0 Hz).
Data are in accordance with previously reported data [7f].
major isomer in the mixture): 1H NMR (300 MHz, CDCl3):
d (ppm)
4.1.11. N-(1-(4-(trifluoromethyl)phenyl)ethyl)-tosylamide (12)
According to the general procedure, the reaction was carried out
in dioxan. Purification by flash column chromatography (silica gel,
EtOAc/heptane 3/7) yielded 12 in 5% yield as a white solid. Mp:
122e123 ꢀC (Lit. no data available).
4.35 (d, J ¼ 5.2 Hz, 2H), 4.80 (br s, 1H), 5.21 (d, J ¼ 10.8 Hz, 5.69 (d,
J ¼ 17.7 Hz, 1H), 6.51 (d, J ¼ 9.2 Hz, 2H), 6.64 (dd, J ¼ 10.8, 17.7 Hz,
1H, 7.16 (m, 1H), 7.19e7.31 (m, 3H), 8.01 (d, J ¼ 9.2 Hz, 2H).
13C NMR (75 MHz, CDCl3):
d (ppm) 47.6, 111.3, 114.6, 125.2, 125.7,
126.4, 126.7, 129.2, 136.3, 137.6, 138.3, 138.4, 153.0.
MS (CI, NH3, neg): m/z (%) 253 (M ꢁ Hꢁ, 100), 137 (10).
19 (mixture of the meta/para isomers):
1H NMR (CDCl3, 500 MHz):
d
(ppm) 1.42 (d, J ¼ 6.8 Hz, 3H), 2.36
(s, 3H), 4.54 (quint, J ¼ 6.9 Hz, 1H), 5.34 (d, J ¼ 7.0 Hz, 1H), 7.12 (d,
J ¼ 8.1 Hz, 2H), 7.21 (d, J ¼ 8.1 Hz, 2H), 7.40 (d, J ¼ 8.1 Hz, 2H), 7.55
(d, J ¼ 8.1 Hz, 2H).
1H NMR (300 MHz, CDCl3):
d (ppm) 1.51 (m, 3H), 4.34 (s, 2H),
4.52 (m, 1H), 4.73 (br s, 1H), 6.37 (m, 2H), 6.48 (m, 2H), 7.16e7.32
13C NMR (CDCl3, 75 MHz):
d (ppm) 21.4, 23.6, 53.4, 125.4 (d, JF-C
(m, 4H), 7.92 (m, 2H), 8.00 (m, 2H).
13C NMR (75 MHz, CDCl3):
d (ppm) 24.6, 47.2, 47.5, 52.9, 53.1,
¼ 3.4 Hz, 2C), 128.5 (d, JF-C ¼ 194.4 Hz), 128.5 (q, JF-C ¼ 426.6 Hz),
126.7 (2C), 127.1 (2C), 129.5, (2C), 137.4, 143.5, 146.0.
111.3, 111.8, 124.4, 125.2, 126.1, 126.2, 126.3, 126.4, 126.5, 128.0,
129.6, 136.7, 138.1, 128.2, 138.3, 143.1, 144.2, 152.1, 153.0.
MS (CI, NH3, neg): m/z (%) 391 (M ꢁ Hꢁ, 100), 137 (10).
4.1.12. N-(1-methyl-1-phenylethyl)-4-nitroaniline (14)
According to the general procedure, the crude product was
purified by flash column chromatography (AcOEt/PE 2/8) to give 14
in 12% yield, as a yellow oil.
4.1.15. N-(cyclohex-2-enyl)-tosylamide (20)
According to the general procedure for hydroamination, the
reaction was carried out with 1,3-cyclohexadiene (95 mL, 1 mmol),
1H NMR (300 MHz, CDCl3) :
d (ppm) 1.63 (s, 6H), 4.90 (broad s,
1H), 6.19 (d, J ¼ 9.2 Hz, 2H), 7.18e7.36 (m, 5H), 7.82 (d, J ¼ 9.2 Hz, 2H).
TsNH2 (856 mg, 5 mmol) and FeCl3 (16 mg, 0.1 mmol) in dioxan
(5 mL) at 80 ꢀC. Purification by flash column chromatography (silica
gel, EtOAc/heptane 3/7) yielded 20 in 44% yield as a white solid.
Mp: 104e105 ꢀC (Lit.20 108e109 ꢀC)
O
1H NMR (CDCl3, 300 MHz):
d (ppm) 1.46e2.00 (m, 6H), 2.42 (s,
O
BnO
BnO
O
BnO
FeCl3•6H2O 10 mol%
DCE, 80°C
O
O
39
OH
+
3H), 3.80 (m, 1H), 4.86 (d, J ¼ 8.5 Hz, 1H), 5.35 (m, 1H), 5.74 (m, 1H),
54%
7:3 dr
BnO
OBn
O
7.29 (d, J ¼ 8.1 Hz, 2H), 7.78 (d, J ¼ 8.1 Hz, 2H).
OBn
10 equiv.
13C NMR (CDCl3, 75 MHz):
d (ppm) 19.2, 21.4, 24.3, 30.0, 48.9,
38
slow addition
126.9 (2C), 127.0, 129.5 (2C), 131.2, 138.3, 143.0.
Scheme 9.
Data are in accordance with previously reported data [19].

302
C.D. Zotto et al. / Journal of Organometallic Chemistry 696 (2011) 296e304
4.1.16. 4-methyl-N-(tetrahydro-2H-pyran-2-yl)
13C NMR (CDCl3, 100 MHz):
d (ppm) 19.0, 19.1, 20.1, 20.6, 29.6,
benzenesulfonamide (21)
29.9, 39.7, 40.1, 52.1, 52.5, 66.8, 67.4, 126.8, 126.9, 127.2, 127.3, 128.5,
128.7, 142.9, 143.2, 168.6, 169.0, 202.3 (2C).
According to the general procedure, compound 21 is obtained in
89% yield as a pale yellow solid after purification by flash chro-
matography on silica gel (Pentane/Ethyl Acetate: 9/1 /8/2).
Data are in accordance with previously reported data [22].
1H NMR (400 MHz, CDCl3):
d
(ppm) 1.38(m, 3H), 1.55 (m, 1H),
4.2.3. 1,3-diphenyl-2-(1-phenylethyl)propane-1,3-dione (27)
The compound (27) was prepared according to the general
protocol on 2 mmol scale. Purified by flash chromatography on
silica gel (Cyclohexane/AcOEt: 8/2) and Kügelrhor distillation.
Yield: 79%.
1.79 (m, 2H), 2.40 (s, 3H), 3.37(m, 1H), 3.69 (d, 1H), 4.75 (td,
J ¼ 2.4 Hz, J ¼ 9.4 Hz, 1H), 5.38 (d, J ¼ 9.4 Hz, 1H), 7.26 (d, J ¼ 8.0 Hz,
2H), 7.79 (d, J ¼ 8.3 Hz, 2H).
13C NMR (100 MHz, CDCl3):
d (ppm) 21.5, 22.3, 24.6, 31.8, 66.1,
82.0, 127.1, 129.3, 138.8, 143.2. Data are in accordance with previ-
ously reported data [20].
1HNMR(CDCl3, 400 MHz):
d
(ppm)1.47(d, J ¼ 7.0 Hz,3H),3.49(dq,
J ¼ 7.0 Hz, J ¼ 10.7 Hz), 5.54 (d, J ¼ 10.5 Hz, 1H), 7.12e7.84 (m, 15H).
13C NMR (CDCl3, 100 MHz):
(ppm): 21.2, 41.9, 60.1, 127.5, 128.5,
d
4.1.17. N-(4-nitrophenyl)tetrahydro-2H-pyran-2-amine (22)
128.6, 133.5, 133.7, 143.9, 195.8, 196.1 (two quaternary aromatic C
signals are not clearly visible in this spectrum.)
To a solution of 4-nitroaniline (279.5 mg, 2 mmol, 1 equiv.) and
iron (III) chloride hexahydrate (59.2 mg, 0.2 mmol, 0.1 equiv.) in
10 mL of 1,4-dioxane at 80 ꢀC was added dropwise by a syringe
pump, over 4 h, the 3,4-Dihydro-2H-pyran (509.7 mg, 6 mmol,
3 equiv.) diluted in 10 mL of 1,4-dioxane. Then, the mixture was
heated at 80 ꢀC for additional 30 mn. The resulting reaction mixture
was concentrated under vacuum and the crude material directly
purified by flash chromatography on silica gel (Pentane/Ether: 9/1
to 7/3) to give the ether-amine 22 (240.8 mg, 54%) as a yellow solid.
Data are in accordance with previously reported data [22].
4.2.4. 3-(1-p-Tolylethyl)pentane-2,4-dione (28)
The compound (28) was prepared according to the general
protocol on 2 mmol scale. Purified by flash chromatography on
silica gel (Cyclohexane/AcOEt: 8/2) and Kügelrhor distillation.
Yield: 64%.
1H NMR (CDCl3, 400 MHz):
d
(ppm) 1.16 (d, J ¼ 7.0 Hz, 3H), 1.81
1H NMR (400 MHz, CDCl3):
d
(ppm) 1.6 (m, 4H), 1.93 (m, 2H),
(s, 3H), 2.23 (s, 3H), 2.31 (s, 3H), 3.56 (dq, J ¼ 6.9 Hz, J ¼ 11.3 Hz),
4.01 (d, J ¼ 11.3 Hz), 7.02e7.14 (m, 4H).
3.58 (m, 1H), 3.97 (m, 1H), 4.72 (m, 1H), 5.04 (br s, 1H), 6.69 (d,
J ¼ 9.2 Hz, 2H), 8.08 (d, J ¼ 9.2 Hz, 2H).
13C NMR (CDCl3, 100 MHz) :
d (ppm) 20.9, 21.1, 29.9 (2C), 40.4,
13C NMR (100 MHz, CDCl3):
d
(ppm) 22.4, 25.0, 31.2, 65.8, 81.3,
76.8, 127.3, 129.8, 137.0, 140.9, 203.2, 203.3.
112.7 (2C), 126.0 (2C), 139.3, 151.2.
Data are in accordance with previously reported data [23].
Data are in accordance with previously reported data [21].
4.2.5. 3-(cyclohex-2-enyl)pentane-2,4-dione (29)
The compound (29) was prepared according to the general
protocol on 2 mmol scale. Purified by flash chromatography on
silica gel (Cyclohexane/AcOEt: 9/1) and Kügelrohr distillation.
Yield: 64%.
4.2. General procedure for the addition of 1,3-dicarbonyl
nucleophiles to olefins
To a solution of b-diketone (20 mmol, 10 equiv.) and iron (III)
chloride hexahydrate (0.1 equiv., finely ground) in 10 ml of
1,4-dioxane was added dropwise by a syringe pump, over 4 h, the
substrate (2 mmol, 1 equiv.) diluted in 10 mL of 1,4-dioxane. The
mixture was then stirred at the indicated temperature during 8 h.
The mixture was then concentrated under vacuum and the crude
material loaded on to a silica gel column and chromatographed
1H NMR (CDCl3, 400 MHz):
d (ppm) 1.10e1.18 (m, 1H), 1.47e1.52
(m, 1H), 1.60e1.69 (m, 2H), 1.90e1.95 (m, 2H), 2.12 & 2.13 (s, 6H),
2.91e3.00 (m, 1H), 3.53e3.56 (d, J ¼ 10.6 Hz, 1H), 5.29e5.33 (m,
1H), 5.68e5.73 (m, 1H).
13C NMR (CDCl3, 100 MHz):
d (ppm) 20.6, 24.8, 26.6, 29.6, 30.1,
35.6, 74.9, 126.9, 130.0, 203.8, 204.1.
with a mixture of Cyclohexane/AcOEt. The mixture of
b
-diketone
Data are in accordance with previously reported data [12].
and product was next purified by Kügelrohr distillation to afford
the desired product.
4.2.6. ethyl 2-(cyclohex-2-enyl)-3-oxobutanoate (30)
The compound (30) was prepared according to the general
protocol on 2 mmol scale. Purified by flash chromatography on silica
gel (Cyclohexane/AcOEt: 8/2) and Kügelrohr distillation. Yield: 40%.
4.2.1. 3-(1-phenylethyl)pentane-2,4-dione (25)
The compound (25) was prepared according to the general
protocol on a 2 mmol scale. Purified by flash chromatography on
silica gel (Cyclohexane/AcOEt: 8/2) and Kügelrhor distillation.
Yield: 86%.
1H NMR (CDCl3, 400 MHz):
d (ppm) 1.20e1.36 (m, 1H), 1.26 (t,
J ¼ 7.1 Hz, 3H), 1.50e1.61 (m, 1H), 1.66e1.79 (m, 2H), 1.92e2.02 (m,
2H), 2.22 & 2.23 (s, 3H), 2.90e2.99 (m, 1H, H2), 3.34 & 3.36 (d & d,
J ¼ 9.8 Hz & J ¼ 10 Hz, 1H), 4.18 (q, J ¼ 7.1 Hz, 2H), 5.42 & 5.49 (ddd &
1H NMR (CDCl3, 400 MHz):
d
(ppm) 1.19 (d, J ¼ 6.8 Hz, 3H), 1.84
(s, 3H), 2.25 (s, 3H), 3.52e3.62 (dq, J ¼ 6.8 Hz, J ¼ 11.3 Hz), 4.00 (d,
ddd, J ¼ 2.0 Hz, J ¼ 4.1 Hz, J ¼ 10.1 Hz
J ¼ 10.0 Hz, 1H), 5.73e5.78 (m, 1H).
&
J ¼ 2.6 Hz, J ¼ 4.7 Hz,
J ¼ 11.3 Hz), 7.11e7.31 (m, 5H).
13C NMR (CDCl3, 100 MHz) :
d
(ppm) 20.8, 29.7, 29.8, 40.4, 76.6,
13C NMR (CDCl3, 100 MHz):
d (ppm) 14.2, 20.8, 20.9, 24.9, 25.0,
126.9, 127.2, 128.8, 142.9, 203.4, 203.5.
26.6, 26.7, 29.5, 29.8, 35.1, 35.2, 61.3, 65.3, 127.3, 127.5, 129.6, 129.8,
168.8, 202.7, 202.9.
Data are in accordance with previously reported data [22].
Data are in accordance with previously reported data [11c].
4.2.2. ethyl 2-acetyl-3-phenylbutanoate (26)
The compound (26) was prepared according to the general
protocol on 2 mmol scale. Purified by flash chromatography on
silica gel (Cyclohexane/AcOEt: 8/2) and Kügelrhor distillation.
Yield: 62%.
4.2.7. 2-(cyclohex-2-enyl)-1,3-diphenylpropane-1,3-dione (31)
The compound (31) was prepared according to the general
protocol on 2 mmol scale. Purified by flash chromatography on
silica gel (Cyclohexane/AcOEt: 8/2) and recristallization in Cyclo-
hexane/Et2O. Yield: 48%.
1H NMR (CDCl3, 400 MHz):
d (ppm) 1,19 (m, 6H), 1.24 (d,
J ¼ 6.9 Hz, 3H), 1.29 (d, J ¼ 6.9 Hz, 3H), 1.92 (s, 3H), 2.29 (s, 3H),
3.49e3.59 (m, 2H), 3.74 (d, J ¼ 11.1 Hz, 1H), 3.80 (d, J ¼ 10.9 Hz, 1H),
3.99 (q, J ¼ 7.1 Hz, 2H), 4.18 (q, J ¼ 7.1 Hz, 2H), 7.15e7.29 (m, 10H).
1H NMR (CDCl3, 400 MHz):
d (ppm) 1.32e1.77 (m, 4H),
2.00e2.04 (m, 2H), 3.49e3.53 (m, 1H), 5.24e5.28 (m, 1H),
5.39e5.80 (m, 2H), 7.39e7.60 (m, 6H), 8.02 (m, 4H).

C.D. Zotto et al. / Journal of Organometallic Chemistry 696 (2011) 296e304
303
13C NMR (CDCl3, 100 MHz):
128.5, 128.6 (4C), 129.2, 133.2, 133.3 (2C), 136.9, 137.0, 194.5, 194.9.
Data are in accordance with previously reported data [13].
d
(ppm) 21.2, 24.9, 27.5, 37.2, 62.5,
(dd, J ¼ 0.8 Hz, J ¼ 2.9 Hz, 1H
a
), 3.87 (m, 1H
& 6H
), 4.57 (dd, J ¼ 4.3 Hz, J ¼ 10.1 Hz,
), 4.69 (dd, J ¼ 1.8 Hz, J ¼ 10.7 Hz, 1H ), 6.99e7.23 (m, 15H
).
13C NMR (CDCl3, 100 MHz):
b), 3.94e4.11 (m, 3Ha &
2Hb
), 4.23e4.46 (m, 6H
a
b
1Ha
a
a &
15H
b
4.2.8. Ethyl 1-(cyclohex-2-enyl)-2-oxocyclopentanecarbo
xylate (32)
d (ppm) 29.5 & 30.4, 29.6 & 30.3,
68.5, 70.0, 70.2,70.5, 71.3, 71.5, 71.7, 71.8, 73.2, 80.0, 81.7, 82.7, 82.8,
82.9, 83.1, 84.8, 85.4, 127.6, 127.7, 127.8, 127.9, 128.3, 128.4, 137.4,
137.5, 138.0, 138.1, 201.7 & 202.8, 202.0 & 202.1.
The compound (32) was prepared according to the general
protocol on 2 mmol scale. Purified by flash chromatography on
silica gel (Cyclohexane/AcOEt: 9/1) and Kügelrohr distillation.
Yield: 14% (1:1 mixture of diastereoisomers).
Acknowledgment
1H NMR (CDCl3, 400 MHz):
d (ppm) 1.21 (m, 3H), 1.42e2.27 (m,
10H), 2.32e2.48 (m, 2H), 3.04e3.16 (m, 1H), 4.06e4.19 (m, 2H), 5.36
& 5.39 (m, 1H), 5.71e5.78 (m, 1H).
We thank the CNRS for financial support.
13C NMR (CDCl3, 100 MHz):
d (ppm) 14.1 (2C), 19.8 & 19.9, 21.9 &
References
22.1, 24.2 & 24.9, 25.0 & 25.5, 28.2 & 28.8, 39.2 (2C), 40.1 & 40.7, 61.5
& 61.6, 64.0 & 64.1, 126.9 & 127.4, 130.0 & 130.7, 173.1 & 173.8, 208.4
and 209.1.
[1] For selected recent iron(III) catalyzed reactions, see: (a) J. Kischel, I. Jovel,
K. Mertins, A. Zapf, M. Beller, Org. Lett. 8 (2006) 19;
(b) B. Bitterlich, K. Schroder, M.K. Tse, M. Beller, Eur. J. Org. Chem. (2008)
4867;
Data are in accordance with previously reported data [12].
(c) K. Cao, F. Zhang, Y. Tu, X. Zhuo, C. Fan, Chem. Eur. J. 15 (2009) 6332;
(d) F. Vallée, J.J. Mousseau, A.B. Charette, J. Am. Chem. Soc. 132 (2010) 1514;
(e) L. Pehlivan, E. Metay, S. Laval, W. Dayoub, P. Demonchaux, G. Mignani,
M. Lemaire, Tetrahedron Lett. 51 (2010) 1939;
(f) A. Guérinot, A. Serra-Muns, C. Gnamm, C. Bensoussan, S. Reymond, J. Cossy,
Org. Lett. 12 (2010) 1808;
4.2.9. 3-(Tetrahydropyran-2-yl)pentane-2,4-dione (34)
The compound (34) was prepared according to the general
protocol on 2 mmol scale. Purified by flash chromatography on silica
gel (Cyclohexane/AcOEt: 8/2) and Kügelrohr distillation. Yield: 54%.
1H NMR (CDCl3, 400 MHz):
d (ppm) 1.14e1.23 (m, 1H), 1.46e1.61
(g) S. Zhang, Y. Tu, C. Fan, F. Zhang, L. Shi, Angew. Chem. Int. Ed. 121 (2009)
8917;
(m, 4H), 1.79 (m, 1H), 2.17 & 2.19 (s & s, 6H), 3.39 (wt, J ¼ 11.3 Hz,
1H), 3.74 (wd, J ¼ 9.6 Hz, 1H), 3.91 (wd, J ¼ 9.9 Hz, 1H), 3.98 (wt,
J ¼ 10.2 Hz, 1H).
(h) S. Biswas, S. Maiti, U. Jana, Eur. J. Org. Chem. (2010) 2861;
(i) W. Chen, R.V. Nguyen, C.J. Li, Tetrahedron 50 (2009) 2895;
(j) C. Dal Zotto, D. Virieux, J.M. Campagne, Synlett (2009) 276;
(k) C. Dal Zotto, J. Wehbe, D. Virieux, J.M. Campagne, Synlett (2008) 2033;
(l) O. Debleds, C. Dal Zotto, E. Vrancken, J.M. Campagne, Adv. Synth. Catal. 351
(2009) 1991.
13C NMR (CDCl3, 100 MHz):
d (ppm): 23.0, 25.6, 29.1, 30.7, 29.8 ,
68.7, 74.9, 76.8, 202.0, 202.9 (2C).
[2] For recent reviews, see: (a) W.M. Czaplik, M. Mayer, J. Cvengros, A. Jacobi von
Wangelin, Chem. Sus. Chem. 2 (2009) 396;
Data are in accordance with previously reported data [11c].
(b) A. Correa, O. García Mancheño, C. Bolm, Chem. Soc. Rev. 37 (2008) 1108.
[3] P.T. Anastas, J.C. Warner, Green Chemistry Theory and Practice. Oxford
University Press, New York, 1998.
[4] For a preliminary account, see: J. Michaux, V. Terrasson, S. Marque, J. Wehbe,
D. Prim, J.M. Campagne Eur. J. Org. Chem. (2007) 2601.
[5] (a) V. Terrasson, S. Marque, M. Georgy, D. Prim, J.M. Campagne, Adv. Synth.
Catal. 348 (2006) 2063;
(b) M. Georgy, V. Boucard, O. Debleds, C. DalZotto, J.M. Campagne, Tetrahe-
dron 65 (2009) 1758.
[6] For a seminal paper dealing with Fe(III)-catalyzed intramolecular hydro-
amination reactions: K. Komeyama, T. Morimoto, T. Kakaki Angew. Chem. Int.
Ed. 45 (2006) 2938.
4.2.10. 1,3-Diphenyl-2-(tetrahydro-2H-pyran-2-yl)propane-1,3-
dione (35)
The compound (35) was prepared according to the general
protocol on 2 mmol scale. Purified by flash chromatography on
silica gel (Cyclohexane/AcOEt: 8/2) and recristallization in Cyclo-
hexane/Et2O. Yield: 58% (yellowish solid).
1H NMR (CDCl3, 400 MHz):
d (ppm) 1.30e1.38 (m, 1H), 1.54e1.61
(m, 2H), 1.78e1.82 (m, 2H), 3.40e3.45 (m, 1H), 3.90e3.94 (m, 1H),
4.91e4.97 (m, 1H), 5.48 (wd, J ¼ 9.2 Hz, 1H), 7.38e7.52 (m, 5H),
7.94e7.98 (m, 5H).
[7] For other metal and TfOH catalyzed hydroamination of styrenes and
1,3-dienes, see: (a) S. Qiu, T. Xu, J. Zhou, Y. Guo, G. Liu, J. Am. Chem. Soc. 132
(2010) 2856;
13C NMR (CDCl3, 100 MHz):
d (ppm) 23.7, 26.3, 36.9, 63.2, 69.2,
(b) M. Kawatsura, J.F. Hartwig, J. Am. Chem. Soc. 122 (2000) 9546;
(c) M. Kawatsura, J.F. Hartwig, J. Am. Chem. Soc. 125 (2003) 14286;
(d) K. Li, P.N. Horton, M.B. Hursthouse, K.K. Hii, J. Organomet. Chem. 665
(2003) 250;
76.8, 133.4, 133.8, 136.8, 137.4 (4C), 150.1 (2C), 193.5, 194.6.
Data are in accordance with previously reported data [11a].
(e) H. Qian, R.A. Widenhoefer, Org. Lett. 7 (2005) 2635;
(f) J.G. Taylor, N. Whittall, K.K. Hii, Org. Lett. 8 (2006) 3561;
(g) L. Yang, L. Xu, W. Zhou, Y. Gao, W. Sun, C. Xia, Synlett (2009) 1167;
(h) N.S. Babu, K.M. Reddy, P.S.S. Prasad, I. Suryanarayana, N. Lingaiah, Tetra-
hedron Lett. 48 (2007) 7642;
(i) D. Jaspers, R. Kubiak, S. Doye, Synlett (2010) 1268;
(j) L. Yang, L. Xu, C. Xia, Tetrahedron Lett. 49 (2008) 2882;
(k) L.T. Kaspar, B. Fingerhut, L. Ackermann, Angew. Chem. Int. Ed. 44 (2005)
5972;
4.2.11. 3-(tetrahydrofuran-2-yl)pentane-2,4-dione (36)
The compound (36) was prepared according to the general
protocol on 2 mmol scale. Purified by flash chromatography on
silica gel (Cyclohexane/AcOEt: 8/2) and Kügelrohr distillation.
Yield: 30% (colorless oil).
1H NMR (CDCl3, 400 MHz):
d (ppm) 1.31e1.34 (m, 1H), 1.78e1.85
(m, 2H), 2.01e2.07 (m, 1H), 2.11 & 2.18 (s & s, 6H), 3.60e3.77 (m,
3H), 4.35e4.40 (m, 1H).
(l) X. Giner, C. Najera, Org. Lett. 10 (2008) 2919;
(m) O. Lober, M. Kawatsura, J.F. Hartwig, J. Am. Chem. Soc. 123 (2001) 4366;
(n) Z. Li, J. Zhang, C. Brouwer, C. Yang, N.W. Reich, C. He, Org. Lett. 8 (2006)
4175;
13C NMR (CDCl3, 100 MHz):
74.0, 77.4, 202.0, 202.7.
d (ppm) 25.1, 29.4, 30.3, 30.0, 67.7,
(o) D.C. Rosenfeld, S. Shekhar, A. Takemiya, M. Utsunomiya, J.F. Hartwig, Org.
Lett. 8 (2006) 4179;
Data are in accordance with previously reported data [11a].
(p) J.G. Taylor, L.A. Adrio, K.K. Hii, Dalton Trans. 39 (2010) 1171;
(q) X. Li, S. Ye, C. He, Z. Yu, Eur. J. Org. Chem. (2008) 4296;
(r) X. Cheng, Y. Xia, H. Wei, B. Xu, C. Zhang, Y. Li, G. Qian, X. Zhang, K. Li, W. Li,
Eur. J. Org. Chem. (2008) 1929;
4.2.12. 3-((3R,4R,5R)-3,4-bis(benzyloxy)-5-(benzyloxymethyl)
tetrahydrofuran-2-yl)pentane-2,4-dione (39)
The compound (39) was prepared according to the general
protocol on 2 mmol scale. Purified by flash chromatography on
silica gel (Cyclohexane/AcOEt: 9/1). Yield: 54% (obtained as
a colorless oil and in a 7:3 dr)
(s) A. Leitner, J. Larsen, C. Steffens, J.F. Hartwig, J. Org, Chem. 69 (2004) 7552.
[8] For the hydroarylation of styrenes, se ref 1a.
[9] J. Michaux. Ph-D thesis Univ Paris Sud Orsay, Nov 2007.
[10] J. Kischel, D. Michalik, A. Zapf, M. Beller, Chem. Asian J. 2 (2007) 909.
[11] For the use of gold, copper, nickel in these reactions: (a) R. Nguyen, X. Yao,
D.S. Bohle, C.J. Li, Org Lett. 7 (2005) 673;
1H NMR (CDCl3, 400 MHz):
& 2.13 (s & s, 6H ), 3.33e3.46 (m, 2H
d
(ppm) 1.88 & 2.15 (s & s, 6H
& 2H ), 3.60 (m, 1H
a
b
), 1.94
), 3.84
b
a
b
(b) Y. Li, Z. Yu, S. Wu, J. Org. Chem. 73 (2008) 5647;

304
C.D. Zotto et al. / Journal of Organometallic Chemistry 696 (2011) 296e304
(c) O.E. Andell, J.E. Baeckvall, C. Moberg, Acta Chem. Scand. B 40 (1986) 184;
(d) for the use of stoichiometric amount of trifluroacetic acid, see:
R. Bihovsky, M.U. Kumar, S. Ding, A. Goyal J. Org. Chem. 54 (1989) 4291.
[17] F. Ragaini, A. Penoni, E. Gallo, S. Tollari, C.L. Gotti, M. Lapadula, E. Mangioni,
a
S. Cenini, Chem. Eur. J. 9 (2003) 249.
[18] T. Soeta, K. Nagai, H. Fujihara, M. Kuriyama, K. Tomioka, J. Org. Chem. 68
(2003) 9723.
[12] Z. Li, C.J. Li, J. Am. Chem. Soc. 128 (2006) 56.
[13] M. Noji, Y. Konno, K. Ishii, J. Org. Chem. 72 (2007) 5161.
[19] M.C. McIntosh, S.M. Weinreb, J. Org. Chem. 58 (1993) 4823.
[20] L. He, J. Yu, J. Zhang, X.-Q. Yu, Org. Lett. 9 (2007) 2277.
[21] A.A. Potekhin, S.L. Zhdanov, V.A. Gindin, K.A. Ogloblin, Zh. Org. Khim 12 (1976)
2090.
[22] J. Kischel, K. Mertins, D. Michalik, A. Zapf, M. Beller, Adv. Synth. Catal. 349
(2007) 865.
[14] For
a related example dealing with activated sugars, see: T. Yamauchi,
M. Shigeta, T. Matsumoto, K. Suzuki Heterocycles 66 (2005) 153.
[15] J.P. Patel, A. Li, H. Dong, V.L. Korlipara, M.J. Mulvihill, Tetrahedron Lett. 50
(2009) 5975.
[16] S.K. Leung, W. Tsui, J. Huang, C. Che, J. Liang, N. Zhu, J. Am. Chem. Soc. 127
(2005) 16629.
[23] X. Yao, C.-J. Li, J. Am. Chem. Soc. 126 (2004) 6884.