Rhodium/Lewis Acid Catalyzed Regioselective Addition of 1,3-Dicarbonyl Compounds to Internal Alkynes

Article abstract of DOI:10.1021/acs.organomet.7b00284

Herein we describe an efficient protocol for the regioselective addition of 1,3-dicarbonyl compounds to internal alkynes catalyzed by rhodium/Lewis acid catalysts. The corresponding branched/linear allylic alkylation products could be selectively obtained in good yields. Rh-H species were considered to be generated by direct C-H oxidative addition of 1,3-dicarbonyl compounds with rhodium catalyst with the assistance of Lewis acid. Moreover, a retro-allylic alkylation process was observed in this transformation.

Full text of DOI:10.1021/acs.organomet.7b00284

Article
pubs.acs.org/Organometallics
Rhodium/Lewis Acid Catalyzed Regioselective Addition of 1,3-
Dicarbonyl Compounds to Internal Alkynes
Wei-Feng Zheng,† Qiu-Jing Xu, and Qiang Kang*
,‡
†
,‡
‡Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Fujian Institute of Research on the Structure of Matter,
Chinese Academy of Sciences, 155 Yangqiao Road West, Fuzhou 350002, People’s Republic of China
†
College of Materials Science and Engineering, Fujian Normal University, 8 Shangsan Road, Fuzhou 350007 People’s Republic of
China
*
S Supporting Information
ABSTRACT: Herein we describe an efficient protocol for the
regioselective addition of 1,3-dicarbonyl compounds to
internal alkynes catalyzed by rhodium/Lewis acid catalysts.
The corresponding branched/linear allylic alkylation products
could be selectively obtained in good yields. Rh−H species
were considered to be generated by direct C−H oxidative
addition of 1,3-dicarbonyl compounds with rhodium catalyst with the assistance of Lewis acid. Moreover, a retro-allylic alkylation
process was observed in this transformation.
INTRODUCTION
Scheme 1. Rhodium-Catalyzed Allylic Alkylation Reactions
■
Transition-metal-catalyzed allylic alkylation reactions have
flourished in the past few decades, which provide an efficient
and powerful tool for constructing allylic C−C bonds.
1
−6
With
the growing attention toward environmental issues, atom-
economical approaches have been welcomed by the synthetic
community. Transition-metal-catalyzed addition of pronucleo-
philes to allenes or alkynes to form allylic C−X bonds (X = N,
O, S) represents one of the most atom-economical approaches
for the synthesis of allylic-substituted compounds. Following
2a,f,7
8
the pioneering work by Trost
and Yamamoto with
palladium catalysts, the seminal work on regioselective
hydrocarboxylation of allene catalyzed by iridium was realized
9
10−12
by Krische in 2008. Recently, Breit and co-workers
developed a series of rhodium-catalyzed pronucleophile
addition reactions to allenes and terminal alkynes toward
branched allylic products.
We speculated that a Lewis acid might increase the acidity of
C−H bond of 1,3-dicarbonyl compounds to assist the oxidative
addition with a Rh complex for the generation of the key Rh−
H intermediate. Herein, we report our recent findings with a
combination of rhodium and Lewis acid as catalyst to promote
the regioselective addition of 1,3-dicarbonyl compounds to
internal alkynes, which allowed access to either the branched or
linear allylic-substituted products (Scheme 1b).
In comparison to the formation of allylic C−X bonds, the
1
3,14
formation of allylic C−C bonds has been less explored.
For
instance, the Breit and Dong groups have independently
reported Rh-catalyzed decarboxylative cross-coupling of β-keto
1
3a
13d,e
acids and allenes
or alkynes
to access branched γ,δ-
unsaturated ketones (Scheme 1a). In these transformations, a
substoichiometric amount of carboxylic acid was required as a
1
5
cocatalyst for the generation of Rh−H species via oxidative
addition of O−H in β-keto acids with an Rh complex. Previous
reported works indicated that the presence of a more acidic O−
H functional group in the pronucleophile or cocatalyst is
necessary for formation of Rh−H species, which might narrow
the substrate scope. Therefore, realizing direct C−H oxidative
addition of carbon pronucleophiles with an Rh complex to
generate a Rh−H species is an important task, which might
enable more possible carbon pronucleophiles in such trans-
formations.
RESULTS AND DISCUSSION
At the outset, acetylacetone (1a) and 1-phenyl-1-propyne (2a)
were chosen as the model substrates to verify our hypothesis. In
the presence of 5 mol % of [Rh(COD)OH] , 12 mol % of dppf,
■
2
and 6 mol % of Yb(OTf) in DCE at 70 °C, the reaction of 1a
3
and 2 equiv of 2a proceeded smoothly to afford the branched
Received: April 13, 2017
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.organomet.7b00284
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Article
product 3a in 75% yield without observation of linear product
Scheme 2. Reaction Substrate Scope: Alkynes
4
a (entry 1, Table 1). However, only a trace amount of 3a was
a
Table 1. Optimization of Reaction Conditions
b
yield
entry
Rh(I)
L
Lewis acid
Yb(OTf)3
(%)
3a/4a
1
2
3
4
5
6
7
8
9
[Rh(COD)OH]2 dppf
[Rh(COD)OH]2 dppf
dppf
75
trace
trace
96
40
6
>95/5
Yb(OTf)3
Yb(OTf)3
Yb(OTf)3
Yb(OTf)3
Yb(OTf)3
Yb(OTf)3
Yb(OTf)3
AlCl3
[Rh(COD)Cl]2
[Rh(NBD)Cl]2
dppf
>95/5
>95/5
>95/5
>95/5
>95/5
>95/5
>95/5
>95/5
>95/5
>95/5
>95/5
>95/5
dppf
Rh(COD) BF4
dppf
2
[Rh(COD)Cl]2
[Rh(COD)Cl]2
[Rh(COD)Cl]2
[Rh(COD)Cl]2
[Rh(COD)Cl]2
[Rh(COD)Cl]2
[Rh(COD)Cl]2
[Rh(COD)Cl]2
[Rh(COD)Cl]2
[Rh(COD)Cl]2
[Rh(COD)Cl]2
DPEphos
Xanphos
BINAP
99
1
79
0
10
11
12
13
14
15
16
17
DPEphos
DPEphos
DPEphos
DPEphos
DPEphos
DPEphos
DPEphos
DPEphos
Gd(OTf)3
Bi(OTf)3
Sc(OTf)3
La(OTf)3
Yb(OTf)3
Yb(OTf)3
Yb(OTf)3
87
34
20
22
20
88
79
c
d
e
f
90/10
72/28
allene, were also examined. In general, branched products with
a terminal alkene were obtained for all of the alkynes tested.
Substrates with phenethyl and a long alkyl chain led to
moderate yields (3e,f). Benzylated and benzoylated alcohols
were tolerated very well to afford 3g,h in 95% and 90% yields,
respectively. A silylated alcohol gave a slightly low yield (76%,
f
a
Reaction conditions: 0.1 mmol of 1a, 0.2 mmol of 2a, 5 mol % of
rhodium catalyst, 12 mol % of ligand, and 6 mol % Lewis acid in 1 mL
of DCE at 70 °C for 24 h. Determined by GC with n-dodecane as
b
c
d
e
internal standard. At 40 °C. 1a/2a = 1/1. 1a/2a = 2/1.
f
1
Determined by H NMR analysis of the crude reaction mixture.
3i), probably due to the instability of TBS under acidic
conditions. A substrate with leaving group (OTs) had no
significant effect on the outcome of the desired product 3j
(80%). Even a free alcohol (2k) could be employed in this
transformation, although a moderate yield was obtained.
Alkynes with other sensitive functionalities such as chloride,
keto, protected amine, and amide also worked well to afford the
branched products in moderate to good yields (3l−o, 47−
97%). However, an aldehyde functionality could not be
tolerated in such a transformation (3p, 0%). This approach
also could be suitable for a complex substrate with a chiral
skeleton, resulting in the corresponding branched alkylated
I
detected in the absence of Lewis acid or Rh precursors (entries
2
and 3, Table 1). Encouraged by these results, further
optimization of the reaction conditions was carried out. We
tested other Rh precursors such as [Rh(COD)Cl] , [Rh-
NBD)Cl] , and Rh(COD) BF together with dppf and found
I
2
(
2 2 4
that the catalyst derived from [Rh(COD)Cl] is the most
2
efficient, affording 3a in 96% GC yield (entry 4, Table 1).
Similarly, the screening of ligands revealed DPEphos to be the
superior ligand for this transformation, resulting in the desired
branched product 3a in an almost quantitative GC yield (entry
, Table 1). Then, various Lewis acids such as AlCl , Gd(OTf) ,
Bi(OTf) , Sc(OTf) , and La(OTf) were examined (entries
16
7
product 3q in 87% yield. Notably, 1-phenyl-1-butyne (2r)
exhibited good reactivity but poor regioselectivity, resulting in
alkylated products 3r,r′ in 88% overall yield with almost 1/1 β/
δ selectivity.
3
3
3
3
3
1
8
0−14, Table 1). The reaction gave the desired product 3a in
7% yield (entry 11, Table 1), while other Lewis acids resulted
in poor yield and no desired product formation was observed
Next, various 1,3-dicarbonyl compounds were employed to
investigate the generality of the current methodology. By
employment of the optimal reaction conditions (entry 7, Table
1, conditions A), the reaction of ethyl-substituted 1,3-diketone
1b with 1-phenyl-1-propyne (2a) gave the alkylated products in
99% yield with 91/9 regioselectivity in favor of branched
product 5a. Increasing the size of the 1,3-diketone only slightly
affected the reactivity of the reaction (5b/6b 91/9, 70% overall
yield). However, the reaction of 1b with aliphatic alkyne 2g
afforded only the branched product 5c in 77% yield without
detection of a linear product. In addition to the 1,3-diketones,
β-keto esters were also suitable substrates to furnish the
branched products 5d,e in 93% and 98% yields, respectively,
albeit with almost 1/1 diastereoselectivity. Interestingly, when
the phenyl-substituted 1,3-diketone 1f was examined under the
with AlCl (entry 10, Table 1). The reaction became sluggish
3
on lowering of the reaction temperature to 40 °C, resulting in a
2
0% GC yield of 3a. Interestingly, by a change in the 1a/2a
ratio of 1/1, both branched and linear product formations were
observed with 90/10 3a/4a in 88% overall yield (entry 16,
Table 1). When 2 equiv of acetylacetone (1a) was employed,
the formation of 4a increased (entry 17, Table 1).
With the optimal reaction conditions in hand (entry 7, Table
), we explored the scope of the coupling reaction with a large
1
number of alkynes 2 (Scheme 2). Alkynes with electron-rich p-
methyl and electron-deficient p-ester or -keto phenyl rings
worked smoothly to afford the allylic alkylated products 3b−d
in 95−99% yields. Aliphatic alkynes, having more than one
possible site for β-H elimination during the formation of the
B
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optimized reaction conditions (conditions A), a mixture of the
branched and linear products (1/16 5f/6f) was obtained in
Scheme 5. Control Experiments
9
3% overall yield. In order to achieve high regioselectivity of
these types of substrates, further optimization reactions were
conducted. We found that in the presence of 5 mol % of
[
Rh(COD)Cl] , 12 mol % of BINAP, and 6 mol % of Sc(OTf)3
2
in DCE at 70 °C for 48 h (conditions B, Scheme 3), the
Scheme 3. Reaction Substrate Scope: 1,3-Dicarbonyl
Compounds
indicated toward a rapid retro-allylic alkylation under reaction
conditions B. The formation of crossover product 3a revealed
17
the involvement of an intermolecular allylic substitution.
However, intramolecular allylic substitution might be faster, as
evidenced by the higher yield of 6f (82% yield), in comparison
to that of 3a (18% yield). To figure out the effect of the
rhodium complex and Lewis acid in the process of retro-allylic
alkylation, several experiments were conducted in the absence
of rhodium complex or Lewis acid. These experiments revealed
that either of them has an effect on the retro-allylic alkylation;
however, the combination of a rhodium complex and Lewis
acid can trigger a faster retro-allylic alkylation (see Figures S14-
S17 in the Supporting Information for more details).
reaction of 1 equiv of 1f with 1 equiv of 1a could afford the
linear product 6f in 90% yield, exclusively. Under reaction
conditions B, various substrates containing either electron-
withdrawing (F, Cl, Br) or electron-donating (Me, OMe)
groups on the phenyl rings afforded the linear products 6g−k
in 63−90% yields. Likewise, 2-naphthyl-substituted 1,3-
diketone 1l was also amenable to alkylation with 2a to afford
6
l in 80% yield.
To get an intuitive understanding of the different
regioselectivities between acetylacetone derivatives and diben-
zoylmethane derivatives, the experiments were carried out and
To evaluate the practicality of this catalytic process, a gram-
scale reaction was carried out. As shown in Scheme 4, the
branched allylic alkylation product 3a could be obtained in 92%
yield under reaction conditions A.
1
monitored by H NMR (see Figure S4, S6, S8, and S10 in the
Supporting Information for more details). With an increase in
the amount of acetylacetone 1a, the yield of linear product 4a
was increased (Figures S4, S6 and S8). We speculated that the
rhodium complex prefers to coordinate with alkyne 2a, thus
hindering the subsequent retro-allylic alkylation. The reaction
profile for the progress of the reaction of dibenzoylmethane
derivative 1k with 2a showed that there was an initial buildup of
the branched product (5k) to reach a peak at around 2 h
followed by its decrease as the thermodynamically stable linear
product (6k) began to form and exist as a major isomer in the
reaction mixture (Figure S10). This observation confirmed that
6k was produced from 5k through a retro-allylic alkylation
process. Due to the conjugation effect, dibenzoylmethane
derivatives might trigger a faster retro-allylic alkylation in
comparison to acetylacetone derivatives.
On the basis of these observations, a catalytic cycle was
proposed as depicted in Scheme 6. Lewis acid activated
substrate 1 would undergo oxidative addition of C−H to the
Rh(I) center, resulting in intermediate A (step I). Then,
Markovnikov-selective hydrometalation delivers the σ-vinyl-
rhodium intermediate B (step II), which may undergo β-
hydride elimination to generate an allene and intermediate A′
(step III). A subsequent Markovnikov-selective hydrometala-
tion of this allene would afford the σ-allylrhodium intermediate
Scheme 4. Gram-Scale Reaction
To gain mechanistic insights into the reaction, the following
control experiments were performed (Scheme 5). First, the
reaction of 1a with 1-phenylallene 7 under the optimal reaction
conditions was performed, affording the corresponding product
3
a in 91% yield (eq a, Scheme 5). This experiment
demonstrated the formation of an allene intermediate from
the alkyne during the course of the reaction. A labeling
experiment was also performed with the deuterated 1-phenyl-1-
propyne 2a-d and 1a under the optimal reaction conditions.
3
The deuterium incorporation was observed at the α, β, and γ
positions of the carbonyl group (eq b, Scheme 5). Next, the
reaction of 1a with mixture of branched/linear products (5f/6f
73/27) was conducted under conditions B (eq c, Scheme 5).
After 48 h, the reaction afforded 6f in 82% yield and 3a in 18%
yield with full conversion of 5f. This crossover experiment
C
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data were obtained on a Bruker Impact II UHR-TOF system. Melting
points were measured on an SGW X-4 apparatus.
Scheme 6. Proposed Catalytic Cycle
General Procedured for the Addition of 1,3-Dicarbonyl
Compound to Internal Alkynes. General Procedure A. In a 10 mL
flame-dried Schlenk tube fitted with a rubber septum and magnetic
bar, [Rh(COD)Cl] (2.5 mg, 0.005 mmol or 5.0 mg, 0.01 mmol),
2
DPEphos (6.5 mg, 0.012 mmol or 13.0 mg, 0.024 mmol), Yb(OTf)3
(3.8 mg, 0.006 mmol or 7.6 mg, 0.012 mmol) were added in the
glovebox and then 1,3-dicarbonyl 1a (0.1 or 0.2 mmol) and internal
alkyne 2a (0.2 or 0.4 mmol) were added by syringe with 1 or 2 mL of
anhydrous dichloroethane (DCE). The tube was sealed and heated to
7
0 °C for 24−48 h. After the reaction was complete (monitored by
TLC), the reaction mixture was directly purified by flash
chromatography on silica gel.
General Procedure B. In a 10 mL flame-dried Schlenk tube fitted
with a rubber septum and magnetic bar, [Rh(COD)Cl] (2.5 mg,
2
0
1
0
.005 mmol or 5.0 mg, 0.01 mmol), BINAP (7.5 mg, 0.012 mmol or
5.0 mg, 0.024 mmol), and Sc(OTf) (3.0 mg, 0.006 mmol or 6.0 mg,
3
.012 mmol) were added in the glovebox and then 1,3-dicarbonyl 1a
(0.1 or 0.2 mmol) and internal alkyne 2a (0.1 or 0.2 mmol) were
added by syringe with 1 or 2 mL of anhydrous dichloroethane (DCE).
The tube was sealed and heated to 70 °C for 48−72 h. After the
reaction was complete (monitored by TLC), the reaction mixture was
directly purified by flash chromatography on silica gel.
C (step IV), which may be attacked by 1 to furnish the desired
branched product 3.
CONCLUSIONS
■
3
-(1-Phenylallyl)pentane-2,4-dione (3a). This compound was
In conclusion, we have developed an efficient approach toward
the regioselective addition of 1,3-dicarbonyl compounds to
internal alkynes to produce allylic alkylated products. The
branched and linear allylic products were selectively obtained in
good to excellent yields by employing 1,3-dicarbonyl
compounds with different substituents. The branched allylic
alkylated products were obtained from 1,3-dicarbonyl com-
pounds with aliphatic substituents, whereas linear allylic
alkylated products were achieved from those aromatic
substituents. Furthermore, a retro-allylic alkylation process
was observed in this protocol. The use of a catalytic amount of
Lewis acid in combination with the rhodium(I) complex was
crucial for success in achieving this transformation. Assisted by
a Lewis acid, direct C−H oxidative addition toward the
rhodium(I) complex might be involved in this transformation.
By alteriation of the reaction conditions, branched and linear
allylic products were selectively obtained. Further exploration
of the rhodium(I)/Lewis acid catalytic system is currently
underway in our laboratory.
prepared according to the general procedure A to provide 3a as a
colorless oil (42.8 mg, 99% yield) after purification by silica gel column
chromatography, with 2−5% EtOAc in PE as eluent (elution gradient).
10b
1
The analytical data of 3a were in agreement with those reported.
H
NMR (400 MHz, CDCl ): δ 7.32−7.27 (m, 2H), 7.23−7.17 (m, 3H),
3
5
.91−5.82 (m, 1H), 5.10−5.05 (m, 2H), 4.26 (d, J = 11.7 Hz, 1H),
4
.19 (dd, J = 11.7, 7.7 Hz, 1H), 2.25 (s, 3H), 1.88 (s, 3H).
3
-(1-(p-Tolyl)allyl)pentane-2,4-dione (3b). This compound was
prepared according to the general procedure A to provide 3b as a
yellow oil (45.5 mg, 99% yield) after purification by silica gel column
chromatography, with 5−7% EtOAc in PE as eluent (elution gradient).
1
H NMR (400 MHz, CDCl ): δ 7.11−7.05 (m, 4H), 5.85 (ddd, J =
3
17.3, 10.2, 7.7 Hz, 1H), 5.08 (m, 2H), 4.24 (d, J = 11.7 Hz, 1H), 4.13
1
3
(dd, J = 11.7, 7.8 Hz, 1H), 2.29 (s, 3H), 2.24 (s, 3H), 1.89 (s, 3H).
NMR (100 MHz, CDCl ): δ 202.9, 202.8, 138.2, 136.8, 136.7, 129.5,
27.7, 116.1, 74.2, 49.4, 29.9, 29.5, 20.9. IR (KBr): 525, 819, 923,
C
3
1
1
[
+
154, 1356, 1513, 1699, 2364, 2924, 3005. HRMS (ESI ): calcd for
+
C H O + Na] , 253.1199; found, 253.1201.
15 18 2
Ethyl 4-(4-Acetyl-5-oxohex-1-en-3-yl)benzoate (3c). This com-
pound was prepared according to the general procedure A to provide
c as a yellow oil (57.0 mg, 99% yield) after purification by silica gel
column chromatography, with 5−7% EtOAc in PE as eluent (elution
3
EXPERIMENTAL SECTION
1
■
gradient). H NMR (400 MHz, CDCl ): δ 7.99 (d, J = 8.4 Hz, 2H),
3
All nonaqueous reactions were performed in oven-dried glassware and
standard Schlenk tubes under an atmosphere of nitrogen. 1,2-
Dichloroethane (DCE), 1,2-dichlorobenzene (ODCB), and acetoni-
trile (CH CN) were distilled from CaH under an inert atmosphere.
7.29 (d, J = 8.3 Hz, 2H), 5.90−5.81 (m, 1H), 5.12 (dd, J = 13.8, 3.3
Hz, 2H), 4.36 (q, J = 7.1 Hz, 2H), 4.32−4.23 (m, 2H), 2.25 (s, 3H),
1.91 (s, 3H), 1.39 (t, J = 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl ): δ
3
202.2, 202.0, 166.1, 149.9, 137.1, 130.0, 129.4, 127.9, 117.1, 73.9, 60.8,
49.4, 29.9, 29.4, 14.2. IR (KBr): 768, 857, 927, 1020, 1106, 1182, 1278,
3
2
Tetrahydrofuran (THF), dioxane, and toluene (PhMe) were distilled
from sodium and benzophenone under an inert atmosphere. All other
solvents and reagents were used as received unless otherwise noted.
Thin-layer chromatography was performed using silica gel 60 F-254
precoated plates (0.2−0.3 mm) and visualized by short-wave UV (254
nm) irradiation, potassium permanganate, CAM, or iodine stain. The
+
1359, 1609, 1716, 2366, 2982. HRMS (ESI ): calcd for [C H O +
Na] , 311.1254; found, 311.1255.
1
7
20
4
+
3-(1-(4-Pentanoylphenyl)allyl)pentane-2,4-dione (3d). This com-
pound was prepared according to the general procedure A to provide
3d as a yellow oil (57.1 mg, 95% yield) after purification by silica gel
1
13
H and C NMR spectra were obtained in CDCl using a Bruker
column chromatography, with 5−7% EtOAc in PE as eluent (elution
3
1
13
1
Avance III spectrometer at 400 and 100 MHz for H and C NMR,
respectively. Chemical shifts (δ) for H NMR spectra are recorded in
gradient). H NMR (400 MHz, CDCl
3
): δ 7.91 (d, J = 8.4 Hz, 2H),
1
7.30 (d, J = 8.4 Hz, 2H), 5.89−5.81 (m, 1H), 5.12−5.08 (m, 2H),
4.31−4.23 (m, 2H), 2.94 (t, J = 7.4 Hz, 2H), 2.25 (s, 3H), 1.92 (s,
3H), 1.74 (p, J = 7.6 Hz, 2H), 1.45 (td, J = 15.0, 7.5 Hz, 2H), 0.96 (t, J
parts per million from tetramethylsilane with the solvent resonance as
the internal standard (chloroform, δ 7.26 ppm). Data are reported as
follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet,
q = quartet, qn = quintet, m = multiplet, and br = broad), coupling
constant in Hz, and integration. Chemical shifts for 13C NMR spectra
are recorded in parts per million from tetramethylsilane using the
central peak of deuteriochloroform (δ 77.00 ppm) as the internal
standard. The infrared spectra were recorded on a VERTEX 70 IR
= 7.4 Hz, 3H). 13C NMR (100 MHz, CDCl ): δ 202.2, 202.1, 199.9,
3
145.1, 137.1, 136.0, 128.6, 128.1, 117.3, 73.9, 49.4, 38.23, 30.0, 29.4,
26.4, 22.4, 13.8. IR (KBr): 926, 1010, 1183, 1267, 1358, 1605, 1699,
+
+
2366, 2958. HRMS (ESI ): calcd for [C H O + Na] , 323.1618;
19
24
3
found, 323.1617.
3-(5-Phenylpent-1-en-3-yl)pentane-2,4-dione (3e). This com-
pound was prepared according to the general procedure A to provide
−1
spectrometer as KBr pellets, with absorption reported in cm . HRMS
D
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13
3
e as a colorless oil (30.7 mg, 63% yield) after purification by silica gel
C NMR (100 MHz, CDCl ): δ 203.0, 202.9, 144.7, 136.9, 132.9,
3
column chromatography, with 9−12% DCM in PE as eluent (elution
129.8, 127.8, 118.5, 74.2, 69.9, 43.6, 30.2, 29.4, 28.1, 26.3, 21.5. IR
(KBr): 555, 664, 816, 927, 1176, 1358, 1699, 2366, 2926. HRMS
1
gradient). H NMR (400 MHz, CDCl ): δ 7.29−7.25 (m, 2H), 7.18
3
+
+
(
5
d, J = 7.2 Hz, 1H), 7.14 (d, J = 7.2 Hz, 2H), 5.60−5.50 (m, 1H),
(ESI ): calcd for [C H O S + Na] , 375.1237; found, 375.1237.
18 24 5
.19−5.12 (m, 2H), 3.70 (d, J = 10.4 Hz, 1H), 2.91 (qd, J = 10.4, 3.0
3-(6-Hydroxyhex-1-en-3-yl)pentane-2,4-dione (3k). This com-
pound was prepared according to the general procedure A to provide
3k as a colorless oil (22.6 mg, 57% yield) after purification by silica gel
Hz, 1H), 2.73−2.64 (m, 1H), 2.52−2.44 (m, 1H), 2.11 (s, 3H), 2.09
13
(
s, 3H), 1.67−1.58 (m, 1H), 1.53−1.44 (m, 1H). C NMR (100
MHz, CDCl ): δ 203.5, 203.3, 141.5, 137.5, 128.4, 128.3, 125.9, 118.4,
3
column chromatography, with 33−35% EtOAc in PE as eluent
1
7
1
2
4.6, 43.9, 34.2, 33.0, 29.9, 29.6. IR (KBr): 700, 47, 923, 1149, 1357,
(
elution gradient). H NMR (400 MHz, CDCl ): δ 5.53−5.43 (m,
3
+
+
455, 1698, 2367, 2928. HRMS (ESI ): calcd for [C H O + Na] ,
16
20
2
1H), 5.12−5.08 (m, 2H), 3.70 (d, J = 10.4 Hz, 1H), 3.64 (t, J = 6.0 Hz,
H), 2.93 (qd, J = 10.3, 2.8 Hz, 1H), 2.21 (s, 3H), 2.11 (s, 3H), 1.72
s, 1H), 1.65−1.58 (m, 1H), 1.51−1.38 (m, 2H), 1.24−1.18 (m, 1H).
13
67.1356; found, 267.1357.
-(Non-1-en-3-yl)pentane-2,4-dione (3f). This compound was
2
(
3
prepared according to the general procedure A to provide 3f as a
colorless oil (18.4 mg, 82% yield) after purification by silica gel column
C NMR (100 MHz, CDCl ): δ 203.7, 203.4, 137.5, 118.1, 74.6, 62.2,
3
4
1
2
3.8, 30.3, 29.7, 29.4, 28.6. IR (KBr): 923, 1153, 1359, 1419, 1541,
chromatography, with 33−35% DCM in PE as eluent (elution
+
+
697, 2363, 2934. HRMS (ESI ): calcd for [C H O + Na] ,
1
11 18
3
gradient). H NMR (400 MHz, CDCl ): δ 5.51−5.42 (m, 1H), 5.09−
3
21.1154; found, 221.1149.
-(6-Chlorohex-1-en-3-yl)pentane-2,4-dione (3l). This compound
5
.05 (m, 2H), 3.68 (d, J = 10.6 Hz, 1H), 2.86 (dd, J = 19.4, 9.6 Hz,
H), 2.20 (s, 3H), 2.10 (s, 3H), 1.28−1.18 (m, 10H), 0.87 (t, J = 6.4
3
1
was prepared according to the general procedure A to provide 3l as a
yellow oil (42.2 mg, 97% yield) after purification by silica gel column
13
Hz, 3H). C NMR (100 MHz, CDCl ): δ 203.7, 203.6, 137.9, 117.6,
3
7
1
4.8, 44.8, 32.5, 31.6, 30.2, 29.5, 28.9, 26.7, 22.5, 14.0. IR (KBr): 1360,
chromatography, with 5−7% EtOAc in PE as eluent (elution gradient).
+
457, 1541, 1558, 1699, 2364, 2857, 2928. HRMS (ESI ): calcd for
1
H NMR (400 MHz, CDCl ): δ 5.53−5.42 (m, 1H), 5.13−5.09 (m,
+
3
[
C H O + Na] , 247.1669; found, 247.1670.
1
4
24
2
2
3
(
H), 3.70 (d, J = 10.5 Hz, 1H), 3.56−3.45 (m, 2H), 2. 93 (qd, J = 10.4,
.1 Hz, 1H), 2.21 (s, 3H), 2.11 (s, 3H), 1.84−1.76 (m, 1H), 1.73−1.66
3
-(6-(Benzyloxy)hex-1-en-3-yl)pentane-2,4-dione (3g). This com-
pound was prepared according to the general procedure A to provide
g as a colorless oil (55.1 mg, 95% yield) after purification by silica gel
13
m, 1H), 1.52−1.44 (m, 1H), 1.30−1.25 (m, 1H). C NMR (100
3
MHz, CDCl ): δ 203.3, 203.1, 137.2, 118.3, 74.5, 44.5, 43.6, 30.0, 29.8,
3
column chromatography, with 5−7% EtOAc in PE as eluent (elution
1
29.5. IR (KBr): 925, 1147, 1358, 1420, 1699, 2367, 2929. HRMS
gradient). H NMR (400 MHz, CDCl ): δ 7.36−7.26 (m, 5H), 5.51−
3
+
+
(
ESI ): calcd for [C H O Cl + Na] , 239.0809; found, 239.0810.
11 17 2
5
1
2
1
2
3
2
3
.42 (m, 1H), 5.09−5.05 (m, 2H), 4.47 (s, 2H), 3.69 (t, J = 10.6 Hz,
H), 3.47−3.38 (m, 2H), 2.92 (qd, J = 10.4, 3.4 Hz, 1H), 2.18 (s, 3H),
.09 (s, 3H), 1.72−1.61 (m, 1H), 1.54−1.48 (m, 1H), 1.43−1.37 (m,
5
-Acetyl-2,2-dimethyl-1-phenyl-4-vinylheptane-1,6-dione (3m).
This compound was prepared according to the general procedure A
to provide 3m as a colorless oil (28.3 mg, 47% yield) after purification
13
H), 1.29−1.22 (m, 1H). C NMR (100 MHz, CDCl ): δ 203.5,
3
by silica gel column chromatography, with 5−7% EtOAc in PE as
03.4, 138.4, 137.6, 128.3, 127.5, 127.5 117.9, 74.6, 72.8, 69.7, 44.1,
0.1, 29.5, 28.9, 26.9. IR (KBr): 698, 739, 923, 1102, 1274, 1358, 1698,
1
eluent (elution gradient). H NMR (400 MHz, CDCl ): δ 7.60−7.58
3
+
+
(m, 2H), 7.47−7.43(m, 1H), 7.38 (t, J = 7.6 Hz, 2H), 5.40−5.30 (m,
365, 2858, 2930. HRMS (ESI ): calcd for [C H O + Na] ,
11.1618; found, 311.1620.
-Acetyl-6-oxo-4-vinylheptyl Benzoate (3h). This compound was
18
24
3
1
2
3
H), 5.02−4.92 (m, 2H), 3.69 (d, J = 10.0 Hz, 1H), 3.10 (qd, J = 10.4,
.7 Hz, 1H), 2.19 (s, 3H), 2.16 (dd, J = 12.0, 3.0 Hz, 1H), 2.06 (s,
5
1
3
H), 1.51 (dd, J = 13.8, 2.6 Hz, 1H) 1.34 (d, J = 2.7 Hz, 6H).
C
prepared according to the general procedure A to provide 3h as a
colorless oil (54.4 mg, 90% yield) after purification by silica gel column
NMR (100 MHz, CDCl ): δ 208.6, 203.4, 203.2, 138.9, 138.2, 130.8,
3
1
28.0, 127.9, 118.2, 74.8, 47.0, 42.6, 42.1, 30.2, 29.9, 28.9, 25.4. IR
chromatography, with 5−7% EtOAc in PE as eluent (elution gradient).
1
(KBr): 1361, 1419, 1473, 1558, 1698, 1733, 2365.98, 2971. HRMS
H NMR (400 MHz, CDCl ): δ 8.03−8.00 (m, 2H), 7.58−7.54 (m,
3
+
+
(
ESI ): calcd for [C H O + Na] , 323.1618; found, 323.1621.
19 24 3
1
4
H), 7.46 (t, J = 7.6 Hz, 2H), 5.55−5.46 (m, 1H), 5.15−5.11 (m, 2H),
.32−4.24 (m, 2H), 3.72 (t, J = 10.4 Hz, 1H), 2.98 (qd, J = 10.3, 3.1
N-(3-Acetyl-4-oxo-2-vinylpentyl)-N-benzyl-4-methylbenzenesul-
fonamide (3n). This compound was prepared according to the general
procedure A to provide 3n as a colorless oil (50.4 mg, 61% yield) after
Hz, 1H), 2.19 (s, 3H), 2.11 (s, 3H), 1.88−1.78 (m, 1H), 1.73−1.62
13
(
m, 1H), 1.54−1.45 (m, 1H), 1.31−1.25 (m, 1H). C NMR (100
purification by silica gel column chromatography, with 9−12% EtOAc
MHz, CDCl ): δ 203.3, 203.2, 166.5, 137.3, 132.9, 130.2, 129.5, 128.3,
3
1
in PE as eluent (elution gradient). H NMR (400 MHz, CDCl ): δ
3
1
1
18.3, 74.5, 64.4, 43.9, 30.1, 29.4, 28.8, 26.1. IR (KBr): 714, 925, 1070,
+
7.67 (d, J = 8.6 Hz, 2H), 7.33−7.28 (m, 7H), 5.68 (dt, J = 17.2, 9.9 Hz,
1H), 4.95 (dd, J = 10.2, 1.2 Hz, 1H), 4.76 (d, J = 17.2 Hz, 1H), 4.50
116, 1275, 1358, 1452, 1717, 2368, 2929. HRMS (ESI ): calcd for
+
[
C H O + Na] , 325.1410; found, 325.1411.
1
8
22
4
(d, J = 14.6 Hz, 1H), 4.10 (d, J = 14.6 Hz, 1H), 3.86 (d, J = 7.0 Hz,
3
-(6-((tert-Butyldimethylsilyl)oxy)hex-1-en-3-yl)pentane-2,4-
1
2
H), 3.31 (dd, J = 14.2, 7.7 Hz, 1H), 2.94 (dd, J = 14.2, 6.8 Hz, 1H),
dione (3i). This compound was prepared according to the general
procedure A to provide 3i as a colorless oil (47.4 mg, 76% yield) after
.72 (m, 1H), 2.44 (s, 3H), 2.06 (s, 3H), 1.94 (s, 3H). 13C NMR (100
MHz, CDCl ): δ 203.9, 203.5, 143.5, 136.2, 136.0, 135.3, 129.7, 128.9,
purification by silica gel column chromatography, with 2−5% EtOAc
3
1
128.6, 128.1, 127.2, 118.9, 68.6, 54.0, 51.7, 43.3, 30.2, 29.4, 21.4. IR
in PE as eluent (elution gradient). H NMR (400 MHz, CDCl ): δ
3
(
KBr): 549, 656, 699, 928, 1159, 1339, 1496, 1699, 2364, 2925.
5
1
2
1
.47 (ddd, J = 18.3, 13.5, 9.4 Hz, 1H), 5.07−5.03 (m, 2H), 3.66 (d, J =
0.6 Hz, 1H), 3.55 (t, J = 6.0 Hz, 2H), 2.89 (qd, J = 10.4, 2.7 Hz, 1H),
.16 (s, 3H), 2.07 (s, 3H), 1.55−1.48 (m, 1H), 1.42−1.32 (m, 2H),
+
+
HRMS (ESI ): calcd for [C H NO S + H] , 414.1734; found,
23 27
4
4
14.1731.
N-(5-Acetyl-6-oxo-4-vinylheptyl)-2,2,2-trifluoroacetamide (3o).
13
.23−1.15 (m, 1H), 0.85 (s, 9H), 0.03 (s, 6H). C NMR (100 MHz,
This compound was prepared according to the general procedure A
to provide 3o as a colorless oil (45.2 mg, 77% yield) after purification
CDCl ): δ 203.6, 203.5, 137.8, 117.8, 74.7, 62.6, 44.2, 30.0, 29.9, 29.6,
3
2
1
3
8.7, 25.9, 18.2, −5.3. IR (KBr): 775, 835, 1099, 1255, 1358, 1472,
+
+
by silica gel column chromatography, with 17−20% EtOAc in PE as
700, 2366, 2857, 2930. HRMS (ESI ): calcd for [C H O Si + Na] ,
17
32
3
1
eluent (elution gradient). H NMR (400 MHz, CDCl ): δ 6.72 (s,
35.2013; found, 335.2014.
-Acetyl-6-oxo-4-vinylheptyl 4-Methylbenzenesulfonate (3j).
3
1
1
2
H), 5.52−5.42 (m, 1H), 5.15−5.08 (m, 2H), 3.71 (d, J = 10.8 Hz,
H), 3.47 (td, J = 13.4, 6.3 Hz, 1H), 3.36 (td, J = 12.4, 5.5 Hz,1H),
.90 (qd, J = 10.4, 2.9 Hz, 1H), 2.20 (s, 3H), 2.11 (s, 3H), 1.68−1.59
5
This compound was prepared according to the general procedure A
to provide 3j as a colorless oil (56.3 mg, 80% yield) after purification
by silica gel column chromatography, with 17−20% EtOAc in PE as
(m, 1H), 1.57−1.45 (m, 1H), 1.39−1.32 (m, 1H), 1.26−1.15 (m, 1H).
1
13
eluent (elution gradient). H NMR (400 MHz, CDCl ): δ 7.77 (d, J =
C NMR (100 MHz, CDCl ): δ 203.6, 203.0, 157.2 (q, J = 36.6 Hz),
3
3
8
(
1
(
.2 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 5.46−5.36 (m, 1H), 5.09−5.02
m, 2H), 4.00−3.96 (m, 2H), 3.65 (d, J = 10.4 Hz, 1H), 2.84 (qd, J =
0.3, 2.9 Hz, 1H), 2.45 (s, 3H), 2.17 (s, 3H), 2.08 (s, 3H), 1.73−1.67
m, 1H), 1.57−1.49 (m, 1H), 1.38−1.30 (m, 1H), 1.23−1.16 (m, 1H).
137.0, 118.6, 115.8 (q, J = 286.3 Hz), 74.1, 43.0, 39.1, 30.5, 29.4, 29.1,
25.8. 19F NMR (376 MHz, CDCl ): δ −75.93. IR (KBr): 1156, 1361,
3
+
1419, 1457, 1508, 1699, 2365, 2940. HRMS (ESI ): calcd for
+
[C H NO F + Na] , 316.1131; found, 316.1133.
13
18
3 3
E
DOI: 10.1021/acs.organomet.7b00284
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
3
- ( 5 - ( ( ( 8 R , 9 S , 1 3 S , 1 4 S ) - 1 3 - M e t h y l - 1 7 - o x o -
(KBr): 701, 758, 921, 1058, 1465, 1696, 1728, 2934, 2973. HRMS
+
+
7
,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]-
(ESI ): calcd for [C H O + Na] , 295.1669; found, 295.1667.
18 24 2
phenanthren-3-yl)oxy)pent-1-en-3-yl)pentane-2,4-dione (3q). This
compound was prepared according to the general procedure A to
provide 3q as a yellow oil (76.1 mg, 87% yield) after purification by
silica gel column chromatography, with 9−12% EtOAc in PE as eluent
elution gradient). H NMR (400 MHz, CDCl ): δ 7.19 (d, J = 8.6 Hz,
4
-(6-(Benzyloxy)hex-1-en-3-yl)heptane-3,5-dione (5c). This com-
pound was prepared according to the general procedure A to provide
c as a colorless oil (49.6 mg, 77% yield) after purification by silica gel
5
column chromatography, with 5−7% EtOAc in PE as eluent (elution
gradient). H NMR (400 MHz, CDCl ): δ 7.36−7.29 (m, 4H), 7.29−
1
1
(
3
3
1
5
1
2
2
1
3
1
4
H), 6.69 (dd, J = 8.6, 2.6 Hz, 1H), 6.61 (d, J = 2.5 Hz, 1H), 5.63−
.52 (m, 1H), 5.14−5.10 (m, 2H), 3.97−3.83 (m, 2H), 3.81 (d, J =
0.4 Hz, 1H), 3.22 (qd, J = 10.0, 3.3 Hz, 1H), 2.90−2.87 (m, 2H),
.53 (dd, J = 18.7, 8.6 Hz, 1H), 2.41−2.37 (m, 1H), 2.23 (s, 3H),
.20−2.15 (m, 1H), 2.13 (s, 3H), 2.12−1.93 (m, 4H), 1.87−1.79 (m,
H), 1.69−1.52 (m, 4H), 1.47−1.38 (m, 2H), 1.25 (s, 1H), 0.91 (s,
7
3
.25 (m, 1H), 5.49−5.40 (m, 1H), 5.09−5.01 (m, 2H), 4.47 (s, 2H),
.70 (d, J = 10.9 Hz, 1H), 3.49−3.37 (m, 2H), 2.95 (qd, J = 10.4, 3.1
Hz, 1H), 2.51−2.38 (m, 4H), 1.70−1.61 (m, 1H), 1.54−1.44 (m, 1H),
1.41−1.33 (m, 1H), 1.24−1.19 (m, 1H), 1.01 (t, J = 7.4 Hz, 3H), 0.97
(t, J = 7.4 Hz, 3H). 13C NMR (100 MHz, CDCl ): δ 206.0, 205.9,
3
138.4, 137.8, 128.2, 127.5, 127.4, 117.7, 73.1, 72.8, 69.7, 44.3, 36.1,
35.7, 29.0, 26.9, 7.4, 7.2. IR (KBr): 698, 737, 921, 1102, 1352, 1456,
H). 13C NMR (100 MHz, CDCl ): δ 220.9, 203.4, 203.4, 156.6,
3
+
+
37.7, 136.9, 132.1, 126.2, 118.5, 114.4, 112.0, 73.9, 64.7, 50.3, 47.9,
3.9, 41.0, 38.3, 35.8, 31.8, 31.5, 29.8, 29.7, 29.6, 26.5, 25.8, 21.5, 13.8.
IR (KBr): 1055, 1159, 1253, 1358, 1499, 1698, 1737, 2366, 2928.
1698, 2857, 2938. HRMS (ESI ): calcd for [C H O + Na] ,
20 28 3
339.1931; found, 339.1930.
Methyl 2-Acetyl-3-phenylpent-4-enoate (5d). This compound was
prepared according to the general procedure A to provide 5d as a
colorless oil (21.6 mg, 93% yield) after purification by silica gel column
+
+
HRMS (ESI ): calcd for [C H O + Na] , 459.2506; found,
28
36
4
4
59.2504.
E)-3-(1-Phenylbut-2-en-1-yl)pentane-2,4-dione (3r). This com-
pound was prepared according to the general procedure A to provide
r as a colorless oil (39.6 mg, 43% yield) after purification by silica gel
(
chromatography, with 33−35% DCM in PE as eluent (elution
1
gradient). Major diastereomer: H NMR (400 MHz, CDCl ): δ 7.31−
3
3
7.28 (m, 2H), 7.23−7.19 (m, 3H), 6.00−5.86 (m, 1H), 5.12−5.05 (m,
column chromatography, with 1−3% EtOAc in PE as eluent (elution
gradient). H NMR (400 MHz, CDCl ): δ 7.29 (t, J = 7.3 Hz, 2H),
2H), 4.15−4.10 (m, 1H), 4.05−3.98 (m, 1H), 3.73 (s, 3H), 1.98 (s,
1
13
3
3H). C NMR (100 MHz, CDCl ): δ 201.4, 168.4, 139.8, 138.1,
3
7
4
5
1
7
.19 (t, J = 9.6 Hz, 3H), 5.55−5.44 (m, 2H), 4.23 (d, J = 11.7 Hz, 1H),
128.8, 127.9, 127.2, 116.3, 64.8, 52.5, 49.5, 29.7. Minor diastereomer:
1
.12(dd, J = 11.6, 7.1 Hz, 1H), 2.23 (s, 3H), 1.87 (s, 3H), 1.61 (d, J =
H NMR (400 MHz, CDCl ): δ 7.31−7.28 (m, 2H), 7.23−7.19 (m,
3
.2 Hz, 3H). 13C NMR (100 MHz, CDCl ): δ 203.0, 202.9, 140.73,
3
3H), 6.00−5.86 (m, 1H), 5.12−5.05 (m, 2H), 4.15−4.10 (m, 1H),
13
30.7, 128.8, 127.7, 127.4, 126.9, 74.6, 49.1, 30.0, 29.5, 17.8. IR (KBr):
00, 755, 967, 1153, 1356, 1453, 1699, 2363, 2919, 3029. HRMS
ESI ): calcd for [C H O + Na] , 253.1199; found, 253.1200.
4.05−3.98 (m, 1H), 3.46 (s, 3H), 2.29 (s, 3H). C NMR (100 MHz,
CDCl ): δ 201.6, 168.1, 140.1, 137.8, 128.6, 127.8, 127.1, 116.7, 65.2,
3
+
+
(
52.3, 49.4, 30.1. IR (KBr): 700, 1157, 1419, 1490, 1541, 1717, 2367,
15
18
2
+
+
(
E)-3-(4-Phenylbut-3-en-2-yl)pentane-2,4-dione (3r′). This com-
2953. HRMS (ESI ): calcd for [C H O + Na] , 255.0992; found,
14 16 3
pound was prepared according to the general procedure A to provide
255.0992.
3
r′ as a colorless oil (41.4 mg, 45% yield) after purification by silica gel
3-Acetyl-3-(1-phenylallyl)dihydrofuran-2(3H)-one (5e). This com-
pound was prepared according to the general procedure A to provide
5e as a colorless oil (24.2 mg, 98% yield) after purification by silica gel
column chromatography, with 33−35% DCM in PE as eluent (elution
column chromatography, with 1−3% EtOAc in PE as eluent (elution
1
gradient). H NMR (400 MHz, CDCl ): δ 7.33−7.26 (m, 4H), 7.24−
3
7
1
(
2
2
2
2
.19 (m, 1H), 6.44 (d, J = 15.9 Hz, 1H), 5.99 (dd, J = 15.9, 8.5 Hz,
H), 3.70 (d, J = 10.3 Hz, 1H), 3.27−3.15 (m, 1H), 2.22 (s, 3H), 2.13
1
gradient). Data for the major diastereomer are as follows. H NMR
s, 3H), 1.08 (d, J = 6.7 Hz, 3H). 13C NMR (100 MHz, CDCl ): δ
3
(400 MHz, CDCl ): δ 7.32−7.26 (m, 3H), 7.15 (d, J = 7.6 Hz, 2H),
3
03.5, 203.4, 136.7, 130.9, 130.9, 128.5, 127.5, 126.2, 75.5, 37.8, 29.9,
9.6, 18.8. IR (KBr): 694, 749, 969, 1155, 1357, 1492, 1698, 2362,
926, 2966, 3026. HRMS (ESI ): calcd for [C H O + Na] ,
6.05−5.91 (m, 1H), 5.28−5.19 (m, 1H), 5.02 (dd, J = 16.9, 0.6 Hz,
1H), 4.42 (d, J = 7.0 Hz, 1H), 4.17−4.07 (m, 2H), 3. 07−2.99 (m,
+
+
13
15
18
2
1H), 2.56−2.49 (m, 1H), 2.22 (s, 3H). C NMR (100 MHz, CDCl ):
3
53.1199; found, 253.1201.
-(1-Phenylallyl)heptane-3,5-dione (5a). This compound was
δ 201.1, 174.7, 137.9, 136.1, 128.9, 128.5, 127.6, 119.4, 66.2, 53.0, 26.5,
24.3. Data for the minor diastereomer are as follows. H NMR (400
1
4
prepared according to the general procedure A to provide 5a as a
colorless oil (24.1 mg, 99% yield) after purification by silica gel column
MHz, CDCl ): δ 7.32−7.26 (m, 5H), 6.05−5.91 (m, 1H), 5.28−5.19
3
(m, 2H), 4.49 (d, J = 8.8 Hz, 1H), 4.00 (q, J = 8.0 Hz, 1H), 3.54 (td, J
chromatography, with 17−20% DCM in PE as eluent (elution
= 8.6, 4.8 Hz, 0.1H), 3.07−2.99 (m, 1H), 2.45 (s, 3H), 2.24−2.16 (m,
1
13
gradient). H NMR (400 MHz, CDCl ) of 5a: δ 7.28 (d, J = 7.4 Hz,
1H). C NMR (100 MHz, CDCl ): δ 201.4, 174.4, 137.5, 134.7,
3
3
2
H), 7.22−7.16 (m, 3H), 5.86 (ddd, J = 17.1, 10.5, 7.2 Hz, 1H), 5.07−
129.1, 128.7, 127.7, 119.0, 66.4, 51.8, 26.2, 25.7. IR (KBr): 703, 931,
+
5
.03 (m, 2H), 4.27−4.18 (m, 2H), 2.61 (qd, J = 7.5, 1.9 Hz, 2H), 2.26
1028, 1162, 1375, 1491, 1712, 1760, 2363, 2920. HRMS (ESI ): calcd
+
(
dq, J = 18.4, 7.4 Hz, 1H), 2.08 (dq, J = 18.4, 7.2 Hz, 1H), 1.03 (t, J =
for [C H O + Na] , 267.0997; found, 267.0992.
15
16
3
1
7
6
3
6
1
.1 Hz, 3H), 0.72 (t, J = 7.2 Hz, 3H). H NMR (400 MHz, CDCl ) of
2-Cinnamyl-1,3-diphenylpropane-1,3-dione (6f). This compound
was prepared according to the general procedure B to provide 6f as a
colorless oil (29.2 mg, 90% yield) after purification by silica gel column
3
a: δ 7.30 (m, 5H), 6.45 (d, J = 15.6 Hz, 1H), 6.09−6.01 (m, 1H),
.84 (t, J = 7.0 Hz, 1H), 2.76 (m, 2H), 2.53−2.42 (m, 4H), 1.05 (t, J =
.8 Hz, 6H). 13C NMR (100 MHz, CDCl ) of 5a: δ 205.3, 140.1,
chromatography, with 2−5% EtOAc in PE as eluent (elution gradient).
3
1
38.2, 128.8, 127.9, 127.1, 116.4, 72.9, 49.8, 36.3, 35.6, 7.3, 7.1. IR
H NMR (400 MHz, CDCl ): δ 7.98 (d, J = 7.8 Hz, 4H), 7.58 (t, J =
3
(
(
KBr): 702, 922, 1101, 1347, 1456, 1699, 1733, 2939, 2979. HRMS
7.2 Hz, 2H), 7.47 (t, J = 7.2 Hz, 4H), 7.26 (d, J = 3.6 Hz, 4H), 7.19−
+
+
ESI ): calcd for [C H O + Na] , 267.1356; found, 267.1359.
7.18 (m, 1H), 6.48 (d, J = 15.8 Hz, 1H), 6.28−6.20 (m, 1H), 5.37 (t, J
16
20
2
= 6.6 Hz, 1H), 3.04 (t, J = 6.9 Hz, 2H). 13C NMR (100 MHz, CDCl ):
2
,6-Dimethyl-4-(1-phenylallyl)heptane-3,5-dione (5b). This com-
pound was prepared according to the general procedure A to provide
b as a colorless oil (19.1 mg, 70% yield) after purification by silica gel
3
δ 195.5, 136.9, 135.9, 133.5, 132.5, 128.9, 128.6, 128.4, 127.3, 126.7,
5
126.1, 57.2, 32.9. IR (KBr): 692, 746, 966, 1263, 1448, 1559, 1696,
+
+
column chromatography, with 17−20% DCM in PE as eluent (elution
gradient). H NMR (400 MHz, CDCl ) of 5b: δ 7.29 (m, 2H), 7.20
2345, 2926, 3026, 3059. HRMS (ESI ): calcd for [C H O + Na] ,
24 20 2
1
3
363.1356; found, 363.1357.
(
m, 3H), 5.89 (ddd, J = 17.2, 10.2, 8.2 Hz, 1H), 5.08 (m, 2H), 4.46 (d,
2-Cinnamyl-1,3-bis(4-fluorophenyl)propane-1,3-dione (6g). This
compound was prepared according to the general procedure B to
provide 6g as a colorless oil (23.7 mg, 63% yield) after purification by
J = 11.8 Hz, 1H), 4.29 (dd, J = 11.2, 8.2 Hz, 1H), 2.90−2.83 (m, 1H),
2
Hz, 3H), 0.63 (d, J = 6.9 Hz, 3H). H NMR (400 MHz, CDCl ) of 6b:
δ 7.29 (m, 5H), 6.45 (d, J = 15.8 Hz, 1H), 6.09 (m, 1H), 4.11 (t, J =
.51−2.42 (m, 1H), 1.09 (dd, J = 15.8, 6.8 Hz, 6H), 0.73 (d, J = 6.8
1
silica gel column chromatography, with 2−5% EtOAc in PE as eluent
3
1
(elution gradient). H NMR (400 MHz, CDCl ): δ 8.00−7.96 (m,
3
13
7
.0 Hz, 1H), 2.79−2.71 (m, 4H), 1.12 (dd, J = 15.6, 6.8 Hz, 12H).
C
2H), 7.90 (d, J = 8.6 Hz, 2H), 7.44 (d, J = 8.5 Hz, 2H), 7.26 (d, J = 4.2
Hz, 4H), 7.23−7.17 (m, 1H), 7.15 (t, J = 8.5 Hz, 2H), 6.47 (d, J = 15.8
Hz, 1H), 6.24−6.16 (m, 1H), 5.23 (t, J = 6.7 Hz, 1H), 3.01 (t, J = 6.6
NMR (100 MHz, CDCl ) of 5b: δ 208.4, 208.3, 140.4, 138.4, 128.7,
1
3
28.3, 127.0, 116.7, 71.5, 50.2, 40.6, 40.3, 18.8, 18.2, 18.1, 17.7. IR
F
DOI: 10.1021/acs.organomet.7b00284
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
Hz, 2H). 13C NMR (100 MHz, CDCl ): δ 194.2, 193.8, 167.3 (d, J =
3
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.organo-
met.7b00284.
■
2
=
55.8 Hz), 140.3, 136.8, 134.2, 132.8, 132.2 (d, J = 2.8 Hz), 131.4 (d, J
9.4 Hz), 129.9, 129.3, 128.5, 127.5, 126.2, 126.1, 116.3 (d, J = 22.0
*
S
19
Hz), 57.6, 32.9. F NMR (376 MHz, CDCl ): δ −103.63 (tt, J = 8.2,
5
2
3
.3 Hz). IR (KBr): 741, 847, 965, 1156, 1234, 1399, 1507, 1595, 1697,
+
+
364, 2926. HRMS (ESI ): calcd for [C H O F + Na] , 399.1167;
24 18 2 2
1
found, 399.1161.
Optimization conditions, synthesis of the substrates, H
NMR monitoring experiments, mechanistic experiments,
1,3-Bis(4-chlorophenyl)-2-cinnamylpropane-1,3-dione (6h). This
compound was prepared according to the general procedure B to
provide 6h as a colorless oil (30.7 mg, 75% yield) after purification by
1
control experiments, characterization data, and H NMR
13
and C NMR spectra of the compounds (PDF)
silica gel column chromatography, with 2−5% EtOAc in PE as eluent
1
(
elution gradient). H NMR (400 MHz, CDCl ): δ 7.89 (d, J = 8.6 Hz,
3
AUTHOR INFORMATION
Corresponding Author
*E-mail for Q.K.: kangq@fjirsm.ac.cn.
ORCID
Qiang Kang: 0000-0002-9939-0875
Notes
The authors declare no competing financial interest.
4
1
1
1
5
H), 7.42 (d, J = 8.6 Hz, 4H), 7.26−7.25 (m, 4H), 7.23−7.17 (m,
■
H), 6.46 (d, J = 15.8 Hz, 1H), 6.23−6.16 (m, 1H), 5.21 (t, J = 6.4 Hz,
H), 3.00 (t, J = 6.7 Hz, 2H). 13C NMR (100 MHz, CDCl ): δ 194.2,
3
40.3, 136.7, 134.2, 132.8, 129.9, 129.3, 128.5, 127.5, 126.1, 126.1,
7.5, 32.9. IR (KBr): 741, 1093, 1263, 1399, 1588, 1697, 2362, 3026.
+
+
HRMS (ESI ): calcd for [C H O Cl + Na] , 431.0576; found,
24
18
2
2
4
31.0573.
,3-Bis(4-bromophenyl)-2-cinnamylpropane-1,3-dione (6i). This
1
compound was prepared according to the general procedure B to
provide 6i as a colorless oil (32.9 mg, 66% yield) after purification by
ACKNOWLEDGMENTS
■
silica gel column chromatography, with 2−5% EtOAc in PE as eluent
This work was supported by the Strategic Priority Research
Program of the Chinese Academy of Sciences, Grant No.
XDB20000000, and the 100 Talents Programme of the Chinese
Academy of Sciences.
1
(
elution gradient). H NMR (400 MHz, CDCl ): δ 7.80 (d, J = 8.6 Hz,
3
4
1
1
H), 7.60 (d, J = 8.6 Hz, 4H), 7.28−7.25 (m, 4H), 7.22−7.17 (m,
H), 6.46 (d, J = 15.6 Hz, 1H), 6.23−6.15 (m, 1H), 5.21 (t, J = 6.7 Hz,
H), 3.00 (t, J = 6.6 Hz, 2H). 13C NMR (100 MHz, CDCl ): δ 194.4,
3
1
5
2
36.7, 134.6, 132.9, 132.3, 130.0, 129.1, 128.5, 127.5, 126.2, 126.0,
7.5, 32.8. IR (KBr): 737, 840, 1008, 1071, 1262, 1396, 1583, 1697,
REFERENCES
■
+
+
363, 3026. HRMS (ESI ): calcd for [C H O Br + Na] , 518.9566;
(1) For selected reviews on transition-metal-catalyzed allylic
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24
18
2
2
found, 518.9564.
2-Cinnamyl-1,3-di-p-tolylpropane-1,3-dione (6j). This compound
was prepared according to the general procedure B to provide 6j as a
colorless oil (27.9 mg, 76% yield) after purification by silica gel column
̈
103, 2921−2944. (c) Helmchen, G.; Dahnz, A.; Dubon, P.; Schelwies,
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chromatography, with 2−5% EtOAc in PE as eluent (elution gradient).
1
H NMR (400 MHz, CDCl ): δ 7.88 (d, J = 8.2 Hz, 4H), 7.26−7.22
3
(
(
6
1
m, 8H), 7.19−7.16 (m, 1H), 6.47 (d, J = 15.8 Hz, 1H), 6.28−6.20
(
g) Koschker, P.; Breit, B. Acc. Chem. Res. 2016, 49, 1524−1536.
(2) For selected recent examples of palladium-catalyzed allylic
m, 1H), 5.30 (t, J = 6.8 Hz, 1H), 3.00 (t, J = 6.8 Hz, 2H), 2.38 (s,
H). 1 C NMR (100 MHz, CDCl ): δ 195.2, 144.4, 137.1, 133.5,
3
3
alkylation to give selectively the branched products, see: (a) Trost, B.
M.; Jakel, C.; Plietker, B. J. Am. Chem. Soc. 2003, 125, 4438−4439.
(b) Zhang, P.; Brozek, L. A.; Morken, J. P. J. Am. Chem. Soc. 2010, 132,
32.2, 129.6, 128.7, 128.4, 127.2, 127.0, 126.1, 57.2, 33.0, 21.6. IR
̈
(
KBr): 741, 818, 964, 1179, 1265, 1559, 1691, 2365, 2920, 3028.
+
+
HRMS (ESI ): calcd for [C H O + Na] , 391.1669; found,
3
26
24
2
1
0686−10688. (c) Chen, J.-P.; Ding, C.-H.; Liu, W.; Hou, X.-L.; Dai,
91.1670.
-Cinnamyl-1,3-bis(4-methoxyphenyl)propane-1,3-dione (6k).
L.−X. J. Am. Chem. Soc. 2010, 132, 15493−15495. (d) Trost, B. M.;
Malhotra, S.; Chan, W. H. J. Am. Chem. Soc. 2011, 133, 7328−7331.
2
This compound was prepared according to the general procedure B
to provide 6k as a colorless oil (36.0 mg, 90% yield) after purification
by silica gel column chromatography, with 9−12% EtOAc in PE as
eluent (elution gradient). H NMR (400 MHz, CDCl ): δ 7.97 (d, J =
(
e) Chen, J.−P.; Peng, Q.; Lei, B.−L.; Hou, X.−L.; Wu, Y.−D. J. Am.
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D. J. Am. Chem. Soc. 2011, 133, 20611−20622.
1
3
(
3) For selected examples of rhodium-catalyzed allylic alkylation to
8
.9 Hz, 4H), 7.27−7.22 (m, 4H), 7.19−7.16 (m, 1H), 6.91 (d, J = 8.9
give selectively the branched products, see: (a) Evans, P. A.; Nelson, J.
D. J. Am. Chem. Soc. 1998, 120, 5581−5582. (b) Evans, P. A.;
Uraguchi, D. J. Am. Chem. Soc. 2003, 125, 7158−7159. (c) Hayashi, T.;
Okada, A.; Suzuka, T.; Kawatsura, M. Org. Lett. 2003, 5, 1713−1715.
d) Ashfeld, B. L.; Miller, K. A.; Martin, S. F. Org. Lett. 2004, 6, 1321−
1324. (e) Evans, P. A.; Lawler, M. J. J. Am. Chem. Soc. 2004, 126,
Hz, 4H), 6.47 (d, J = 15.8 Hz, 1H), 6.28−6.20 (m, 1H), 5.23 (t, J = 6.5
Hz, 1H), 3.83 (s, 6H), 3.00 (t, J = 6.8 Hz, 2H). 13C NMR (100 MHz,
CDCl ): δ 194.1, 163.8, 137.1, 132.2, 130.9, 129.0, 128.4, 127.2, 127.1,
1
1
Na] , 423.1567; found, 423.1568.
-Cinnamyl-1,3-bis(naphthalen-2-yl)propane-1,3-dione (6l). This
compound was prepared according to the general procedure B to
3
26.1, 114.0, 57.2, 55.5, 33.1. IR (KBr): 745, 842, 1027, 1168, 1261,
(
+
599, 1685, 2365, 2839, 2935. HRMS (ESI ): calcd for [C H O +
26
24
4
+
8
4
2
642−8643. (f) Kazmaier, U.; Stolz, D. Angew. Chem., Int. Ed. 2006,
5, 3072−3075. (g) Evans, P. A.; Oliver, S.; Chae, J. J. Am. Chem. Soc.
012, 134, 19314−19317.
2
provide 6l as a colorless oil (35.3 mg, 80% yield) after purification by
(
4) For selected examples of iridium-catalyzed regioselective allylic
silica gel column chromatography, with 5−7% EtOAc in PE as eluent
alkylation, see: (a) Lipowsky, G.; Miller, N.; Helmchen, G. Angew.
Chem., Int. Ed. 2004, 43, 4595−4597. (b) Obora, Y.; Hatanaka, S.;
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W.−B.; Dai, L.−X.; Helmchen, G.; You, S.−L. J. Am. Chem. Soc. 2011,
133, 19006−19014. (d) Liu, W.−B.; Zheng, C.; Zhuo, C.−X.; Dai, L.−
X.; You, S.−L. J. Am. Chem. Soc. 2012, 134, 4812−4821. (e) Hamilton,
J. Y.; Sarlah, D.; Carreira, E. M. Angew. Chem., Int. Ed. 2013, 52, 7532−
7535. (f) Liu, W.−B.; Reeves, C. M.; Virgil, S. C.; Stoltz, B. M. J. Am.
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Am. Chem. Soc. 2013, 135, 2068−2071. (h) Krautwald, S.; Sarlah, D.;
1
(
elution gradient). H NMR (400 MHz, CDCl ): δ 8.55 (s, 2H), 8.06
3
(
dd, J = 8.6, 1.4 Hz, 2H), 7.88−7.80 (m, 6H), 7.60 (t, J = 7.6 Hz, 2H),
7
1
1
1
1
1
.52 (t, J = 7.6 Hz, 2H), 7.24 (dt, J = 14.8, 6.7 Hz, 4H), 7.18−7.14 (m,
H), 6.54 (d, J = 15.8 Hz, 1H), 6.38−6.30 (m, 1H), 5.66 (t, J = 6.7 Hz,
H), 3.18 (t, J = 6.8 Hz, 2H). 13C NMR (100 MHz, CDCl ): δ 195.5,
3
36.9, 135.7, 133.4, 132.5, 132.4, 130.5, 129.7, 128.9, 128.8, 128.4,
27.7, 127.3, 126.9, 126.8, 126.1, 124.1, 57.7, 33.2. IR (KBr): 745, 820,
+
123, 1176, 1278, 1466, 1689, 2366, 3057. HRMS (ESI ): calcd for
+
[
C H O + Na] , 463.1669; found, 463.1665.
3
2
24
2
G
DOI: 10.1021/acs.organomet.7b00284
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
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DOI: 10.1021/acs.organomet.7b00284
Organometallics XXXX, XXX, XXX−XXX