Pd-Catalyzed Regioselective Hydroesterification of Olefins with 2,2,2-Trifluoroethyl Formate

Article abstract of DOI:10.1002/ejoc.201901601

A Pd-catalyzed regioselective hydroesterification of olefins with 2,2,2-trifluoroethyl formate (TFEF) is described. Either linear or branched esters can be selectively obtained with proper ligands in most cases. The reaction process is operationally simple and involves no toxic CO gas.

Full text of DOI:10.1002/ejoc.201901601

DOI: 10.1002/ejoc.201901601
Full Paper
Regioselective Hydroesterification
Pd-Catalyzed Regioselective Hydroesterification of Olefins with
2
,2,2-Trifluoroethyl Formate
Jinhua Chen,[
a][‡]
Minyan Huang,
[a][‡]
Wenlong Ren, Jianxiao Chu, and Yian Shi*
[a]
[a]
[a,b]
Abstract: A Pd-catalyzed regioselective hydroesterification of proper ligands in most cases. The reaction process is operation-
olefins with 2,2,2-trifluoroethyl formate (TFEF) is described. Ei- ally simple and involves no toxic CO gas.
ther linear or branched esters can be selectively obtained with
Introduction
Results and Discussion
In our previous studies, we have shown that styrenes can be
Carboxylic esters are an important class of compounds and are
of great significance for pharmaceuticals, fine chemicals, and
organic synthesis. As an effective approach to this class of com-
pounds, hydroesterification of olefins has been actively investi-
regioselectively hydroesterified with HCO Ph to give either lin-
2
ear or branched esters, respectively, with 1,1′-bis(dicyclohexyl-
phosphino)-ferrocene or 2-(dicyclohexyl-phosphino)biphenyl as
[
5e]
[
1,2]
[3]
ligand. In current studies, several alkyl formates (4a–g) were
gated with
made in use of formates as CO surrogates primarily with Ru
or without CO gas. Much efforts have been
[
4]
first examined for the hydroesterification with styrene in the
[
5]
presence of 5 mol% Pd(OAc) and 10 mol% 1,1′-bis(dicyclohex-
and Pd catalysts. For the Pd-catalyzed hydroesterification
process, alkyl formates have been found to be generally much
less effective than aryl formates for the reaction. For example,
no ester products were observed for the hydroesterification
2
5e,6]
[
ylphosphino)-ferrocene (L1)
Table 1, entries 1–7). Poor reactivities were observed with
HCO Me (4a) and HCO Et (4b) (Table 1, entries 1 and 2). A mix-
in toluene at 80 °C for 48 h
(
2
2
[
5a,5c]
ture of esters 2a and 3a were formed in 47 and 38 % yield,
respectively, with HCO CH Ph (4c) and HCO CH CO Me (4d)
reactions with alkyl formates such as HCO Bn,
2
[
5a]
[5c]
[5a,5e]
HCO C H Ph,
HCO Et,
and HCO nBu.
As part of our
2
2
2
2
2
2
2
4
2
2
(
Table 1, entries 3 and 4). Interestingly, with fluoroethyl for-
continuing interest in hydroesterification process (Scheme 1),
we have investigated a number of electronically different for-
mates with aim of understanding the influencing factors for the
reactivity and expanding the reaction to other esters. Our stud-
ies have shown that the electronic nature of the formate has
profound impact on the reaction reactivity and selectivity. 2,2,2-
Trifluoroethyl formate (HCO CH CF ) has been found to be
mates (4e, f, g), both yield and regioselectivity were increased
as more F was introduced (Table 1, entries 5–7). Linear ester 2a
was formed in 84 % yield with >20:1 l/b ratio when
HCO CH CF (4g) was used. The dramatic increase of l/b ratio
2
2
3
from 1:1 to >20:1 with addition of F was particularly notewor-
thy. With HCO CH CF (4g), additional ligands were investi-
2
2
3
2
2
3
gated for the hydroesterification (Table 1, entries 8–18). Little
hydroesterification reaction occurred with ligands such as dppe
and tris(4-fluorophenyl)-phosphine (L4) (Table 1, entries 8 and
highly effective agent for the hydroesterification of olefins. Ei-
ther linear or branched 2,2,2-trifluoroethyl esters can be ob-
tained regioselectively with proper ligands. Herein, we wish to
report our preliminary results on this subject.
1
5). In other cases, a mixture of linear and branched esters were
formed in varying yields (Table 1, entries 9–17). The regioselec-
tivity was reversed with 2-(dicyclohexyl-phosphino)biphenyl
[
5e,7]
(L7)
(Table 1, entry 18). Branched ester 3a was isolated in
3
2 % yield with l/b ratio <1:20. It was found that the reaction
can be greatly boosted by adding small amounts of H O. The
2
exact role of H O is not clear at this moment. Ester 3a was
2
Scheme 1. Pd-Catalyzed Hydroesterification of Olefins.
formed in 94 % yield under proper reaction conditions (Table 1,
entry 22).
The hydroesterification process with 2,2,2-trifluoroethyl for-
mate (HCO CH CF ) can be extended to a variety of substituted
[
a] Institute of Natural and Synthetic Organic Chemistry,
Changzhou University
2
2
3
Changzhou 213164, China
E-mail: Yian.Shi@colostate.edu
styrenes. With ligand L1 (Method A), linear trifluoromethyl aryl
propionates can be obtained in 38–82 % yields with >20:1 l/b
ratio (Table 2, entries 1–13). The phenyl rings can bear various
[
[
b] Department of Chemistry, Colorado State University
Fort Collins, Colorado 80523, United States
‡] These two authors contributed equally.
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejoc.201901601.
substituents including OMe, F, Cl, and CF groups. 2-Vinylpyr-
3
idine and N-vinylphthalimide were found to be effective sub-
strates, giving the corresponding esters in 56 % and 90 % yield,
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Table 1. Studies of the Reaction Conditions.[a]
Scheme 2. Pd-Catalyzed Hydroesterification of Acetylenes.
As exemplified by styrene, the reaction process can be car-
ried out on a gram scale with both Method A and Method B
Entry
Ligand
HCO
2
R
Yield (%)[b] (2a/3a)[c]
(Scheme 3). Linear ester 2a and branched ester 3a were ob-
1
2
3
4
5
6
7
8
9
L1
L1
L1
L1
L1
L1
L1
dppe
dppp
dppb
dppf
L2
P(p-tolyl)
L3
L4
L5
L6
L7
L7
HCO
HCO
HCO
HCO
HCO
HCO
HCO
4g
4g
4g
4g
4g
4g
4g
4g
4g
4g
4g
4g
2
2
2
2
2
2
Me (4a)
Et (4b)
CH
CH
CH
CH
trace
0
47 (1:2)
38 (1:1)
tained in 80 % and 77 % yield, respectively, with high regio-
selectivity.
2
2
2
2
Ph (4c)
CO
CH
2
Me (4d)
F (4e)
2
33 (1:1)
CHF
CF
2
(4f)
(4g)
76 (18:1)
84 (> 20:1)
trace
90 (2.5:1)
83 (1.7:1)
47 (1.6:1)
98 (1:1.4)
73 (1.6:1)
70 (2.2:1)
trace
8 (1:1.3)
28 (1.1:1)
32 (< 1:20)
37 (< 1:20)
39 (< 1:20)
80 (< 1:20)
94 (< 1:20)
80 (< 1:20)
2
CH
2
3
1
1
1
1
1
1
1
1
1
1
2
2
0
1
2
3
4
5
6
7
8
9
0
1
3
Scheme 3. Gram-Scale Hydroesterification of Olefin.
A precise reaction mechanism is not clear at this moment
and await further study. One plausible catalytic cycle is shown
in Scheme 4 as previously suggested for the hydroesterification
[
[
[
d]
d]
d]
L7
L7
L7
L7
4g (add 5 % HCOOH)
4g (add 10 μL H O)
4g (add 15 μL H O)
4g (add 30 μL H
4g (add 10 % F
2
[
d]
d]
d]
[5e]
0
2
2
2
with HCO Ph.
The Pd was first oxidatively added to
2
[
[
2
2
3
4
2
O)
HCO CH CF (4g) to form complex 5, which gave complex 6
2
2
3
L7
3
CCH
2
OH) 37 (< 1:20)
R (1.50 mmol),
(0.025 mmol), ligand (0.050 or 0.10 mmol, P/Pd = 4:1) in toluene
0.10 mL) at 80 °C for 48 h unless otherwise stated. [b] The yield was deter-
after rearrangement. The hydropalladation of the olefin by 6
led to complexes 7 and 8, which underwent migratory insertion
to form acyl Pd complexes 9 and 10. Upon reductive elimina-
tion, 9 and 10 were converted to esters 2 and 3, respectively,
[
a] The reactions were carried out with 1a (0.50 mmol), HCO
2
Pd(OAc)
(
2
1
mined from the crude reaction mixture by H NMR with BnOMe as an internal
standard. [c] The ratio of 2a:3a was determined by 1H NMR analysis of the
crude reaction mixture. [d] L7 (0.15 mmol) at 80 °C for 24 h.
respectively, with >20:1 regioselectivity (Table 2, entries 14 and
15). For alkyl terminal olefin 1-pentadecene, the linear ester was
obtained in 40 % yield with >20:1 l/b ratio (Table 2, entry 16).
As shown in Scheme 2, the reaction can also apply to certain
alkyne. α,ꢀ-Unsaturated trifluoroethyl ester 2q was isolated in
[
8]
84 % yield from diphenyl acetylene (1q).
A mixture of
regioisomers (2r/2r′ = 1:1.8) was obtained in 90 % yield with
[
9]
1-phenylpropyne (1r).
With ligand L7 (Method B), branched trifluoromethyl aryl
propionates were obtained in 32–91 % yields with 1:14 to <1:20
l/b ratio for styrenes (Table 2, entries 1–12). For sterically bulky
2,4,6-trimethylstyrene, a mixture of linear and branched esters
was obtained in 30 % yield with 3.4:1 l/b ratio (Table 2, entry
1
1
3). No ester was obtained with 2-Vinylpyridine (Table 2, entry
4). For N-vinylphthalimide, the linear ester was isolated in 29 %
yield (Table 2, entry 15). 1-Pentadecene was not effective sub-
strate under the reaction conditions (Table 2, entry 16).
Scheme 4. Proposed Catalytic Pathways of Hydroesterification.
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2 2 3
Table 2. Pd-Catalyzed Hydroesterification of Olefins with HCO CH CF (TFEF) (4g).
[
a] Method A: The reactions were carried out with 1 (0.50 mmol), HCO
2
CH
2
CF
3
(TFEF) (4g) (1.50 mmol), Pd(OAc)
2
(0.025 mmol), and L1 (0.050 mmol) in
toluene (0.1 mL) at 80 °C for 48 h unless otherwise stated. Method B: The reactions were carried out with 1 (0.50 mmol), HCO
Pd(OAc) (0.025 mmol), L7 (0.15 mmol), and H O (15 μL) in toluene (0.1 mL) at 80 °C for 24 h unless otherwise stated. [b] Isolated yield. The ratio of 2:3 was
determined by 1H NMR analysis of the crude reaction mixture. [c] At 120 °C.
2 2 3
CH CF (TFEF) (4g) (1.50 mmol),
2
2
with the Pd0 catalyst being regenerated. In general, was performed on silica gel (300–400 mesh). H NMR spectra were
1
recorded on a 400 MHz NMR spectrometer, 1 C NMR spectra were
3
HCO CH CF displayed similar behavior to HCO Ph for the reac-
tion process.
2
2
3
2
recorded on a 100 MHz NMR spectrometer and 19F NMR spectra
were recorded on a 376 MHz NMR spectrometer. IR spectra were
recorded on a FT-IR spectrometer. Melting points were uncorrected.
HCO Me (4a), and HCO Et (4b) were purchased from commercial
2
2
Conclusions
suppliers. Formates 4c and 4d, were prepared from HCO H, Ac O,
2
2
the corresponding alcohols, and NaOAc based on the reported pro-
In summary, we have found that 2,2,2-trifluoroethyl formate
4g) is a highly effective reagent for hydroesterification of ole-
[
11]
cedure.
For 4d 1 mol-% Bu NI was also added after the addition
4
(
of NaOAc. Formates 4e, 4f, and 4g were prepared by heating
fins. A variety of linear or branched 2,2,2-trifluoroethyl esters
can be obtained with high regioselectivity by the choice of
proper ligand. The reaction is operationally simple and involves
no handling of toxic CO. The current reaction process provides
a viable route for the synthesis of various 2,2,2-trifluoroethyl
esters, which can serve as reactive intermediate in organic syn-
HCO H and the corresponding alcohols at 80 °C for 18 h based on
2
[12]
the reported procedure.
Representative Procedure for Hydroesterification (Table 2)
Method A: To a mixture of Pd(OAc) (0.0056 g, 0.025 mmol), ligand
2
[
10]
thesis. Further understanding of the reaction mechanism and L1 (0.0289 g, 0.050 mmol), and toluene (0.1 mL) in a sealed tube
development of more effective hydroesterification process with (2.0 mL) were added styrene (1a) (0.0521 g, 0.50 mmol) and 2,2,2-
broad substrate scope will be pursued.
trifluoroethyl formate (4g) (0.192 g, 1.5 mmol) successively via syr-
inge. Upon purging with Ar to remove the air, the tube was tightly
sealed with a Teflon cap. The reaction mixture was stirred at 80 °C
for 48 h, cooled to room temp., and purified by flash chromatogra-
phy (silica gel, petroleum ether/diethyl ether = 100:3) to give ester
2a as light yellow oil (0.0905 g, 78 % yield) (The solvent was evapo-
rated in an ice water bath to reduce the loss of the ester product
Experimental Section
General Methods: All commercially available reagents were used
without further purification. All solvents used for the reaction were
purified with solvent purification system. Column chromatography due to its volatility).
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Method B: To a mixture of Pd(OAc) (0.0056 g, 0.025 mmol), ligand
6.95 (m, 3H), 4.43 (q, J = 8.5 Hz, 2H), 2.93 (t, J = 7.6 Hz, 2H), 2.71 (t,
2
L7 (0.0526 g, 0.150 mmol), H O (15 μL), and toluene (0.1 mL) in a
J = 8.0 Hz, 2H), 2.31 (s, 3H); 13C NMR (100 MHz, CDCl ) δ = 171.4,
2
3
sealed tube (2.0 mL) were added styrene (1a) (0.0521 g, 0.50 mmol)
and 2,2,2-trifluoroethyl formate (4g) (0.192 g, 1.5 mmol) succes- (q, J = 36.3 Hz), 35.4, 30.7, 21.5; HRMS (EI) Calcd for C H F O [M] :
139.9, 138.4, 129.2, 128.7, 127.4, 125.4, 123.2 (q, J = 275.2 Hz), 60.4
+
12 13 3 2
sively via syringe. Upon purging with Ar to remove the air, the tube
was tightly sealed with a Teflon cap. The reaction mixture was
stirred at 80 °C for 24 h, cooled to room temp., quenched with 30 %
H O (0.20 mL), stirred at rt for 10 min to oxidize the ligand (L7),
and purified by flash chromatography (silica gel, petroleum ether/
diethyl ether = 100:3) to give ester 3a as light yellow oil (0.0882 g,
246.0862, found 246.0864.
Ester 2i (Table 2, entry 9): Light yellow oil; IR (film): 1760,
–
1 1
1
6
7
1
8
085 cm ; H NMR (400 MHz, CDCl ) δ = 7.32–7.20 (m, 1H), 7.02–
3
2
2
.94 (m, 1H), 6.94–6.86 (m, 2H), 4.45 (q, J = 8.4 Hz, 2H), 2.97 (t, J =
.6 Hz, 2H), 2.74 (t, J = 7.7 Hz, 2H); 13C NMR (100 MHz, CDCl ) δ =
3
71.1, 163.1 (d, J = 244.3 Hz), 142.5 (d, J = 7.3 Hz), 130.3 (d, J =
.2 Hz), 124.1 (d, J = 2.7 Hz), 123.1 (q, J = 275.4 Hz), 115.4 (d, J =
7
6 % yield).
Ester 2a[
1
13]
(Table 2, entry 1): Light yellow oil; IR (film): 1758,
21.1 Hz), 113.6 (d, J = 20.8 Hz), 60.5 (q, J = 36.4 Hz), 35.0, 30.4 (d,
J = 1.5 Hz); HRMS (EI) Calcd for C H F O [M] : 250.0611, found
–
1
1
+
171 cm ; H NMR (400 MHz, CDCl ) δ = 7.32–7.26 (m, 2H), 7.24–
3
11 10 4 2
7
.16 (m, 3H), 4.44 (q, J = 8.5 Hz, 2H), 2.97 (t, J = 7.6 Hz, 2H), 2.73 (t, 250.0613.
13
J = 8.0 Hz, 2H); C NMR (100 MHz, CCl ) δ = 171.4, 140.0, 128.8,
3
Ester 2j (Table 2, entry 10): Light yellow oil; IR (film): 1758,
1
28.4, 126.7, 123.1 (q, J = 275.5 Hz), 60.5 (q, J = 36.4 Hz), 35.4, 30.8;
F NMR (376 MHz, CDCl ) δ = –73.8; HRMS (EI) Calcd for C H F O
11 11 3 2
–
1 1
19
1169 cm ; H NMR (400 MHz, CDCl ) δ = 7.26–7.16 (m, 3H), 7.11–
3
3
+
7.05 (m, 1H), 4.45 (q, J = 8.4 Hz, 2H), 2.95 (t, J = 7.6 Hz, 2H), 2.73 (t,
[M] : 232.0706, found 232.0709.
J = 7.8 Hz, 2H); 13C NMR (100 MHz, CDCl ) δ = 171.1, 142.0, 134.5,
3
Ester 2b (Table 2, entry 2): Light yellow oil; IR (film): 1760,
130.0, 128.6, 126.9, 126.7, 123.1 (q, J = 275.4 Hz), 60.5 (q, J =
–1 1
1
171 cm ; H NMR (400 MHz, CDCl ) δ = 7.16–7.08 (m, 4H), 4.47
+
3
36.4 Hz), 35.0, 30.4; HRMS (EI) Calcd for C H ClF O [M] : 266.0316,
11 10 3 2
(
2
1
q, J = 8.5 Hz, 2H), 2.96 (t, J = 7.5 Hz, 2H), 2.74 (t, J = 8.0 Hz, 2H),
found 266.0318.
Ester 2k (Table 2, entry 11): White solid; mp. 49.0–49.7 °C; IR (film):
.34 (s, 3H); 13C NMR (100 MHz, CDCl ) δ = 171.5, 136.9, 136.2, 129.5,
3
28.3, 123.1 (q, J = 275.7 Hz), 60.5 (q, J = 36.3 Hz), 35.6, 30.4, 21.2;
–
1 1
+
1760, 1169 cm ; H NMR (400 MHz, CDCl
3
) δ = 7.90–7.75 (m, 3H),
HRMS (EI) Calcd for C H F O [M] : 246.0862, found 246.0864.
12 13 3 2
7.67 (s, 1H), 7.53–7.42 (m, 2H), 7.35 (dd, J = 8.4, 1.6 Hz, 1H), 4.48 (q,
Ester 2c (Table 2, entry 3): Light yellow oil; IR (film): 1760,
13
J = 8.5 Hz, 2H), 3.17 (t, J = 7.6 Hz, 2H), 2.86 (t, J = 7.9 Hz, 2H);
C
–
1 1
1
6
2
1
3
2
175 cm ; H NMR (400 MHz, CDCl ) δ = 7.16–7.10 (m, 2H), 6.87–
3
NMR (100 MHz, CDCl ) δ = 171.4, 137.4, 133.7, 132.4, 128.5, 127.8,
3
.82 (m, 2H), 4.45 (q, J = 8.5 Hz, 2H), 3.79 (s, 3H), 2.93 (t, J = 7.6 Hz,
H), 2.72 (t, J = 7.8 Hz, 2H); C NMR (100 MHz, CDCl ) δ = 171.5,
58.4, 132.0, 129.4, 123.1 (q, J = 275.4 Hz), 114.1, 60.4 (q, J =
6.2 Hz), 55.4, 35.7, 29.9; HRMS (EI) Calcd for C H F O [M] :
127.7, 127.0, 126.7, 126.3, 125.7, 123.1 (q, J = 275.4 Hz), 60.5 (q, J =
1
3
3
+
36.4 Hz), 35.3, 30.9; HRMS (EI) Calcd for C H F O [M] : 282.0862,
1
5 13 3 2
found 282.0863.
+
1
2 13 3 3
Ester 2l (Table 2, entry 12): Light yellow oil; IR (film): 1762,
62.0811, found 262.0814.
–
1 1
1
184 cm ; H NMR (400 MHz, CDCl ) δ = 7.21–7.13 (m, 4H), 4.49
3
Ester 2d (Table 2, entry 4): Light yellow oil; IR (film): 1762,
(
2
q, J = 8.4 Hz, 2H), 3.00 (t, J = 7.6 Hz, 2H), 2.72 (t, J = 7.5 Hz, 2H),
.35 (s, 3H); C NMR (100 MHz, CDCl ) δ = 171.6, 138.1, 136.1, 130.6,
–1 1
1
173 cm ; H NMR (400 MHz, CDCl ) δ = 7.37–7.31 (m, 2H), 7.19–
3
13
3
7
.12 (m, 2H), 4.47 (q, J = 8.5 Hz, 2H), 2.97 (t, J = 7.6 Hz, 2H), 2.75 (t,
128.6, 126.8, 126.4, 123.1 (q, J = 275.4 Hz), 60.5 (q, J = 36.4 Hz),
1
3
J = 7.4 Hz, 2H), 1.32 (s, 9H); C NMR (100 MHz, CDCl ) δ = 171.6,
3
+
34.1, 28.2, 19.4; HRMS (EI) Calcd for C H F O [M] : 246.0862,
1
2 13 3 2
1
3
2
49.5, 136.9, 128.1, 125.7, 123.1 (q, J = 276.1 Hz), 60.5 (q, J =
found 246.0865.
+
6.5 Hz), 35.4, 34.6, 31.5, 30.3; HRMS (EI) Calcd for C H F O [M] :
1
5 19 3 2
88.1332, found 288.1334.
Ester 2m (Table 2, entry 13): Light yellow solid; mp. 45.3–45.6 °C;
IR (film): 1746, 1271, 1163 cm ; H NMR (400 MHz, CDCl ) δ = 6.87
–
1 1
3
Ester 2e (Table 2, entry 5): Light yellow oil; IR (film): 1760,
–1
1
(s, 2H), 4.52 (q, J = 8.5 Hz, 2H), 3.05–2.93 (m, 2H), 2.60–2.51 (m, 2H),
1
259 cm ; H NMR (400 MHz, CDCl ) δ = 7.21–7.13 (m, 2H), 7.02–
3
2
.32 (s, 6H), 2.27 (s, 3H); 13C NMR (100 MHz, CDCl ) δ = 171.7, 136.2,
3
6
.94 (m, 2H), 4.45 (q, J = 8.5 Hz, 2H), 2.96 (t, J = 7.6 Hz, 2H), 2.73 (t,
13
136.1, 133.6, 129.3, 123.2 (q, J = 275.3 Hz), 60.5 (q, J = 36.4 Hz),
J = 7.7 Hz, 2H); C NMR (100 MHz, CDCl ) δ = 171.3, 161.8 (d, J =
3
+
33.1, 24.6, 21.0, 19.8; HRMS (EI) Calcd for C H F O [M] : 274.1175,
14 17 3 2
2
2
42.8 Hz), 135.6 (d, J = 3.2 Hz), 129.9 (d, J = 7.8 Hz), 123.1 (q, J =
found 274.1176.
75.4 Hz), 115.6 (d, J = 21.1 Hz), 60.5 (q, J = 36.4 Hz), 35.5, 30.0;
+
HRMS (EI) Calcd for C H F O [M] : 250.0611, found 250.0614.
Ester 2n (Table 2, entry 14): Light yellow oil; IR (film): 1730,
11 10 4 2
–
1 1
1
161 cm ; H NMR (400 MHz, CDCl ) δ = 8.52–8.48 (m, 1H), 7.58
Ester 2f (Table 2, entry 6): Light yellow oil; IR (film): 1760,
3
–1
1
(td, J = 7.7, 1.8 Hz, 1H), 7.16 (d, J = 7.8 Hz, 1H), 7.13–7.08 (m, 1H),
.44 (q, J = 8.5 Hz, 2H), 3.13 (t, J = 7.4 Hz, 2H), 2.92 (t, J = 7.3 Hz,
1
173 cm ; H NMR (400 MHz, CDCl ) δ = 7.29–7.23 (m, 2H), 7.16–
3
4
7
.10 (m, 2H), 4.45 (q, J = 8.4 Hz, 2H), 2.95 (t, J = 7.6 Hz, 2H), 2.72 (t,
13
13
2H); C NMR (100 MHz, CDCl ) δ = 171.7, 159.4, 149.5, 136.6, 123.2,
J = 7.7 Hz, 2H); C NMR (100 MHz, CDCl ) δ = 171.1, 138.4, 132.5,
3
3
123.1 (q, J = 275.6 Hz), 121.7, 60.4 (q, J = 36.4 Hz), 32.8, 32.6; HRMS
1
29.8, 128.9, 123.1 (q, J = 275.5 Hz), 60.5 (q, J = 36.4 Hz), 35.2, 30.1;
+
+
(ESI) Calcd for C H F NO [M + H] : 234.0736, found 234.0735.
HRMS (EI) Calcd for C H ClF O [M] : 266.0316, found 266.0318.
10 11 3 2
11
10
3 2
Ester 2g (Table 2, entry 7): Light yellow oil; IR (film): 1764,
Ester 2o (Table 2, entry 15): White solid; mp. 99.4–99.6 °C; IR (film):
–1
1
–1 1
1
7
2
1
106 cm ; H NMR (400 MHz, CDCl ) δ = 7.56 (d, J = 8.0 Hz, 2H),
1758, 1715, 1175 cm ; H NMR (400 MHz, CDCl
3
) δ = 7.87–7.79 (m,
3
.32 (d, J = 8.0 Hz, 2H), 4.46 (q, J = 8.4 Hz, 2H), 3.05 (t, J = 7.6 Hz,
2H), 7.75–7.68 (m, 2H), 4.45 (q, J = 8.4 Hz, 2H), 4.01 (t, J = 7.0 Hz,
1
3
13
H), 2.78 (t, J = 7.6 Hz, 2H); C NMR (100 MHz, CDCl ) δ = 171.0,
2H), 2.83 (t, J = 7.0 Hz, 2H); C NMR (100 MHz, CDCl
) δ = 169.5,
3
3
44.1, 129.1 (q, J = 32.3 Hz), 128.9, 125.7 (q, J = 3.6 Hz), 124.4 (q,
168.1, 134.3, 132.1, 123.6, 123.0 (q, J = 275.4 Hz), 60.8 (q, J =
+
J = 270.0 Hz), 123.1 (q, J = 275.4 Hz), 60.6 (q, J = 36.4 Hz), 34.9, 36.5 Hz), 33.6, 32.6; HRMS (ESI) Calcd for C13
H F KNO [M + K] :
10 3 4
+
3
0.5; HRMS (EI) Calcd for C H F O [M] : 300.0580, found
340.0194, found 340.0193.
1
2 10 6 2
3
00.0582.
Ester 2p (Table 2, entry 16): Light yellow solid; mp. 27.3–27.5 °C; IR
–
1 1
Ester 2h (Table 2, entry 8): Light yellow oil; IR (film): 1758,
(film): 1760, 1173 cm ; H NMR (400 MHz, CDCl ) δ = 4.45 (q, J =
3
–
1 1
1
169 cm ; H NMR (400 MHz, CDCl ) δ = 7.22–7.14 (m, 1H), 7.06–
8.5 Hz, 2H), 2.40 (t, J = 7.5 Hz, 2H), 1.72–1.57 (m, 2H), 1.32–1.21 (m,
3
Eur. J. Org. Chem. 0000, 0–0
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2
1
2
4H), 0.87 (t, J = 6.4 Hz, 3H); 13C NMR (100 MHz, CDCl ) δ = 172.4, 275.6 Hz), 60.6 (q, J = 36.2 Hz), 45.2, 21.6, 18.6; HRMS (ESI) Calcd for
3
–
23.2 (q, J = 275.4 Hz), 60.3 (q, J = 36.2 Hz), 33.8, 32.2, 29.9, 29.89, C H F O [M – H] : 245.0795, found 245.0791.
12 12 3 2
9.86, 29.8, 29.6, 29.59, 29.4, 29.2, 24.9, 22.9, 14.3; HRMS (EI) Calcd
Ester 3i (Table 2, entry 9): Light yellow oil; IR (film): 1762,
+
for C H F O [M] : 338.2427, found 338.2429.
–1 1
18
33
3
2
1
173 cm ; H NMR (400 MHz, CDCl ) δ = 7.34–7.24 (m, 1H), 7.11–
3
Ester 3a[
14]
(Table 2, entry 1): Light yellow oil; IR (film): 1756,
7.05 (m, 1H), 7.05–6.93 (m, 2H), 4.57–4.48 (m, 1H), 4.48–4.38 (m, 1H),
–
1
1
13
1
4
7
1
167 cm ; H NMR (400 MHz, CDCl ) δ = 7.37–7.23 (m, 5H), 4.54–
3.83 (q, J = 7.2 Hz, 1H), 1.54 (d, J = 7.2 Hz, 3H); C NMR (100 MHz,
3
.42 (m, 1H), 4.42–4.31 (m, 1H), 3.81 (q, J = 7.2 Hz, 1H), 1.53 (d, J = CDCl
) δ = 172.6, 163.1 (d, J = 244.9 Hz), 141.8 (d, J = 7.3 Hz), 130.4
3
.2 Hz, 3H); 13C NMR (100 MHz, CDCl ) δ = 173.2, 139.5, 128.9, 127.7, (d, J = 8.2 Hz), 123.4 (d, J = 2.9 Hz), 123.0 (q, J = 275.7 Hz), 114.8
3
19
27.65, 123.1 (q, J = 275.5 Hz), 60.6 (q, J = 36.3 Hz), 45.3, 18.5;
F
(d, J = 3.8 Hz), 114.6 (d, J = 2.7 Hz), 60.8 (q, J = 36.5 Hz), 45.0, 18.4;
–
NMR (376 MHz, CDCl ) δ = –73.8; HRMS (EI) Calcd for C H F O
HRMS (ESI) Calcd for C11
H F O [M – H] : 249.0544, found 249.0541.
9 4 2
3
11 11 3 2
+
[M] : 232.0706, found 232.0708.
Ester 3j (Table 2, entry 10): Light yellow oil; IR (film): 1758,
–
1 1
Ester 3b (Table 2, entry 2): Light yellow oil; IR (film): 1760,
1171 cm ; H NMR (400 MHz, CDCl
2H), 7.22–7.15 (m, 1H), 4.57–4.46 (m, 1H), 4.46–4.35 (m, 1H), 3.80 (q,
J = 7.2 Hz, 1H), 1.54 (d, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl
δ = 172.6, 141.4, 134.7, 130.2, 128.0, 127.9, 125.9, 123.0 (q, J =
3
) δ = 7.3 (s, 1H), 7.29–7.23 (m,
–1 1
1
7
1
169 cm ; H NMR (400 MHz, CDCl ) δ = 7.22–7.16 (m, 2H), 7.16–
3
.10 (m, 2H), 4.55–4.42 (m, 1H), 4.42–4.29 (m, 1H), 3.78 (q, J = 7.2 Hz,
3
)
1
3
H), 2.32 (s, 3H), 1.52 (d, J = 7.2 Hz, 3H); C NMR (100 MHz, CDCl3)
δ = 173.3, 137.4, 136.6, 129.6, 127.5, 123.1 (q, J = 275.6 Hz), 60.6 (q, 275.7 Hz), 60.7 (q, J = 36.4 Hz), 44.9, 18.4; HRMS (ESI) Calcd for
+
–
J = 36.3 Hz), 44.8, 21.2, 18.5; HRMS (EI) Calcd for C H F O [M] :
C
11
H
9
ClF
O [M – H] : 265.0249, found 265.0245.
3 2
1
2 13 3 2
2
46.0862, found 246.0863.
Ester 3k (Table 2, entry 11): Light yellow oil; IR (film): 1758,
–
1 1
1
169 cm ; H NMR (400 MHz, CDCl ) δ = 7.89–7.81 (m, 3H), 7.78 (s,
Ester 3c (Table 2, entry 3): Light yellow oil; IR (film): 1756,
3
–1
1
1H), 7.55–7.44 (m, 3H), 4.63–4.50 (m, 1H), 4.49–4.36 (m, 1H), 4.02 (q,
J = 7.2 Hz, 1H), 1.67 (d, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3)
δ = 173.2, 136.9, 133.6, 132.9, 128.7, 128.0, 127.8, 126.5, 126.49,
1
6
1
167 cm ; H NMR (400 MHz, CDCl ) δ = 7.25–7.18 (m, 2H), 6.89–
3
.82 (m, 2H), 4.53–4.41 (m, 1H), 4.41–4.29 (m, 1H), 3.76 (q, J = 7.2 Hz,
H), 3.75 (s, 3H), 1.50 (d, J = 7.2 Hz, 3H); C NMR (100 MHz, CDCl3)
1
3
1
26.2, 125.7, 123.1 (q, J = 275.6 Hz), 60.7 (q, J = 36.4 Hz), 45.4, 18.6;
δ = 173.3, 159.1, 131.6, 128.6, 123.1 (q, J = 275.5 Hz), 114.2, 60.5 (q,
J = 36.2 Hz), 55.2, 44.3, 18.4; HRMS (ESI) Calcd for C H F O [M –
H] : 261.0744, found 261.0741.
–
HRMS (ESI) Calcd for C H F O [M – H] : 281.0795, found 281.0792.
15 12
3 2
1
2 12 3 3
–
Ester 3l (Table 2, entry 12): Light yellow oil; IR (film): 1760,
–
1 1
1
169 cm ; H NMR (400 MHz, CDCl ) δ = 7.28–7.23 (m, 1H), 7.23–
Ester 3d (Table 2, entry 4): Light yellow oil; IR (film): 1758,
3
–1
1
7.13 (m, 3H), 4.57–4.45 (m, 1H), 4.45–4.32 (m, 1H), 4.06 (q, J = 7.1 Hz,
H), 2.38 (s, 3H), 1.52 (d, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3)
δ = 173.4, 138.1, 136.0, 130.8, 127.5, 126.7, 126.6, 123.1 (q, J =
75.6 Hz), 60.5 (q, J = 36.3 Hz), 41.0, 19.7, 17.8; HRMS (EI) Calcd for
1
7
280 cm ; H NMR (400 MHz, CDCl ) δ = 7.35 (d, J = 8.2 Hz, 2H),
3
1
.23 (d, J = 8.2 Hz, 2H), 4.58–4.45 (m, 1H), 4.42–4.29 (m, 1H), 3.80
q, J = 7.2 Hz, 1H), 1.53 (d, J = 7.2 Hz, 3H), 1.31 (s, 9H); 1 C NMR
3
(
(
2
100 MHz, CDCl ) δ = 173.4, 150.6, 136.4, 127.3, 125.9, 123.0 (q, J =
3
+
C H F O [M] : 246.0862, found 246.0866.
2
75.6 Hz), 60.6 (q, J = 36.4 Hz), 44.8, 34.7, 31.5, 18.5; HRMS (ESI)
12 13 3 2
–
Calcd for C H F O [M – H] : 287.1264, found 287.1262.
15
18
3
2
Ester 2q (Scheme 2): Light green solid; mp. 70.5–70.9 °C; IR (film):
–
1 1
1
760, 1165 cm ; H NMR (400 MHz, CDCl ) δ = 7.92 (s, 1H), 7.42–
3
Ester 3e (Table 2, entry 5): Light yellow oil; IR (film): 1760,
–1
1
7.34 (m, 3H), 7.28–7.20 (m, 3H), 7.20–7.13 (m, 2H), 7.10–7.03 (m, 2H),
1
6
1
1
1
4
2
165 cm ; H NMR (400 MHz, CDCl ) δ = 7.31–7.24 (m, 2H), 7.06–
3
4
.59 (q, J = 8.4 Hz, 2H); 13C NMR (100 MHz, CDCl ) δ = 166.3, 142.6,
3
.98 (m, 2H), 4.55–4.45 (m, 1H), 4.45–4.34 (m, 1H), 3.81 (q, J = 7.2 Hz,
H), 1.53 (d, J = 7.2 Hz, 3H); C NMR (100 MHz, CDCl ) δ = 173.0,
62.3 (d, J = 244.4 Hz), 135.2 (d, J = 3.2 Hz), 129.3 (d, J = 8.0 Hz),
23.1 (q, J = 275.6 Hz), 115.8 (d, J = 21.3 Hz), 60.7 (q, J = 36.3 Hz),
4.5, 18.5; HRMS (ESI) Calcd for C H F O [M – H] : 249.0544, found
1
3
135.1, 134.3, 131.0, 129.9, 129.8, 129.0, 128.5, 128.4, 123.3 (q, J =
3
2
+
75.7 Hz), 61.1 (q, J = 36.4 Hz); HRMS (EI) Calcd for C H F O [M
H] : 307.0940, found 307.0939.
17 14 3 2
+
–
1
1 9 4 2
Esters 2r and 2r′ (Scheme 2): Light yellow liquid; IR (film): 1729,
–
1 1
49.0541.
1168 cm ; H NMR (400 MHz, CDCl ) (small amount of pure 2r′)
3
δ = 7.78 (q, J = 1.5 Hz, 1H), 7.45–7.32 (m, 5H), 4.60 (q, J = 8.4 Hz, 2H),
Ester 3f (Table 2, entry 6): Light yellow oil; IR (film): 1758,
2.16 (d, J = 1.5 Hz, 3H); 13C NMR (100 MHz, CDCl
) (small amount
–1
1
3
1
7
1
1
3
2
173 cm ; H NMR (400 MHz, CDCl ) δ = 7.34–7.28 (m, 2H), 7.26–
3
of pure 2r′) δ = 167.1, 141.3, 135.5, 130.0, 129.1, 128.7, 126.9, 123.4
(q, J = 275.4 Hz), 61.0 (q, J = 36.4 Hz), 14.2; HRMS (ESI) Calcd for
.21 (m, 2H), 4.55–4.45 (m, 1H), 4.45–4.35 (m, 1H), 3.80 (q, J = 7.2 Hz,
1
3
H), 1.53 (d, J = 7.2 Hz, 3H); C NMR (100 MHz, CDCl ) δ = 172.8,
3
+
C H F O [M + H] : 245.0784, found 245.0782.
1
2 12 3 2
37.9, 133.6, 129.1, 129.07, 123.0 (q, J = 275.5 Hz), 60.7 (q, J =
–
6.3 Hz), 44.7, 18.5; HRMS (ESI) Calcd for C H ClF O [M – H] :
1
1
9
3 2
65.0249, found 265.0247.
Acknowledgments
We gratefully acknowledge the National Natural Science Foun-
dation of China (21632005, 21472083) and Changzhou Univer-
sity for financial support.
Ester 3g (Table 2, entry 7): Light yellow oil; IR (film): 1762,
–1 1
1
081 cm ; H NMR (400 MHz, CDCl ) δ = 7.61 (d, J = 8.2 Hz, 2H),
3
7
.43 (d, J = 8.1 Hz, 2H), 4.57–4.47 (m, 1H), 4.47–4.37 (m, 1H), 3.90
1
3
(q, J = 7.2 Hz, 1H), 1.58 (d, J = 7.2 Hz, 3H); C NMR (100 MHz, CDCl3)
δ = 172.5, 143.4, 130.1 (q, J = 32.6 Hz), 128.2, 126.0 (q, J = 3.7 Hz),
1
4
2
24.3 (q, J = 270.2 Hz), 123.0 (q, J = 275.5 Hz), 60.8 (q, J = 36.5 Hz), Keywords: Hydroesterification · Regioselectivity · 2,2,2-
–
5.1, 18.4; HRMS (ESI) Calcd for C H F O [M – H] : 299.0512, found
1
2
9
6
2
Trifluoroethyl formate · Olefins
99.0509.
Ester 3h (Table 2, entry 8): Light yellow oil; IR (film): 1764,
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1] For leading reviews on hydroesterification in the presence of CO gas,
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1
7
1
165 cm ; H NMR (400 MHz, CDCl ) δ = 7.25–7.18 (m, 1H), 7.13–
3
.05 (m, 3H), 4.58–4.45 (m, 1H), 4.45–4.31 (m, 1H), 3.79 (q, J = 7.2 Hz,
1
3
H), 2.34 (s, 3H), 1.53 (d, J = 7.2 Hz, 3H); C NMR (100 MHz, CDCl3)
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Eur. J. Org. Chem. 0000, 0–0
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% and 1 mol-% Pd(OAc)
2
.
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minor isomer was tentatively assigned to regioisomer 2r based on the
NMR of the mixture.
2
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Received: October 31, 2019
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© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
Regioselective Hydroesterification
J. Chen, M. Huang, W. Ren,
J. Chu, Y. Shi* ....................................... 1–7
Pd-Catalyzed Regioselective Hy-
droesterification of Olefins with
2,2,2-Trifluoroethyl Formate
A Pd-catalyzed regioselective hydro- esters can be selectively obtained with
esterification of olefins with 2,2,2-tri- proper ligands in most cases. The reac-
fluoroethyl formate (TFEF) is de- tion process is operationally simple
scribed. Either linear or branched and involves no toxic CO gas.
DOI: 10.1002/ejoc.201901601
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© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim