Synthesis of phthalic acid derivatives: Via Pd-catalyzed alkoxycarbonylation of aromatic C-H bonds with alkyl chloroformates

Article abstract of DOI:10.1039/c8cc06663a

A Pd(ii)-catalyzed alkoxycarbonylation of aromatic C-H bonds with alkyl chloroformates has been developed. A broad range of benzamides and alkyl chloroformates are compatible with this protocol. The reaction is operationally simple and scalable. The direct group could be readily removed to access substituted phthalic acid esters (PAEs), 1,2-dibenzyl alcohols and phthalamides. Besides alkoxycarbonylation of benzamide β-C-H bonds, γ-alkoxycarbonylation of 2-phenylacetamide is also feasible.

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DOI: 10.1039/C8CC06663A
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Synthesis of Phthalic Acid Derivatives via Pd-Catalyzed
Alkoxycarbonylation of Aromatic C–H Bonds with Alkyl
Chloroformates
Gang Liao,a Hao-Ming Chen,b and Bing-Feng Shi*a
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
5
A Pd(II)-catalyzed alkoxycarbonylation of aromatic C-H
and synthetic applications of C−H carbonylation reactions, the
bonds with alkyl chloroformates has been developed. A broad 50 discovery of new type of surrogates that can be easily applied to
range of benzamides and alkyl chloroformates are compatible
the divergent and expeditious synthesis of various carboxylic
esters is still highly demanded. In this context, alkyl
chloroformates are especially promising alkoxycarbonyl
surrogates since they are readily available and operationally simple.
10 with this protocol. The reaction is operationally simple and
scalable. The direct group could be readily removed to access
substituted phthalic acid esters (PAEs), 1,2-dibenzyl alcohols
and phthalamides. Besides alkoxycarbonylation of benzamide 55 In 2009, Kakiuchi and co-workers reported the first Ru-catalyzed
β-C–H bonds, γ-alkoxycarbonylation of 2-phenylacetamide is
15 also feasible.
alkoxycarbonylation
of
2-arylpyridines
with
alkyl
chloroformates.[19] However, the pyridyl directing group can’t be
removed or modified. Inspired by this elegant work, we have
recently
achieved
the
Pd(II)-catalyzed
stereoselective
alkyl
Aromatic esters are a privileged scaffold in natural products,
agrochemicals, pharmaceuticals, and materials science. They are
also widely used as versatile building blocks for various organic
transformations.[1] Traditional methods, such as the condensation
20 of activated acid derivatives with alcohols, the reaction of
organometallic compounds with di-tert-butyl dicarbonate, and
transition metal-catalyzed coupling of aryl halides with carbon
monoxide or its precursors, have been widely used for the
preparation of these scaffolds.[2] Recently, the direct introduction
25 of a carbonyl group into organic molecules through transition
metal-catalyzed C−H activation have attracted tremendous
attentions.[3,4] In particular, direct carbonylation of inert C–H
bonds with carbon monoxide (CO) has been extensively studied
and found great applications in the synthesis of amides/lactams,[5]
30 carboxylic acids,[6] and esters.[7-9] Although carbon monoxide is
one of the most inexpensive and abundant C1 building block, there
are several major limitations hurdle its use in laboratory-scale,
such as the toxicity, gaseous form and flammability. Thus, the
development of C–H alkoxycarbonylation reactions with
35 esterification reagents other than carbon monoxide is highly
desirable.
60 alkoxycarbonylation of C(sp3)–H bonds with
chloroformates.[20] In consideration of the importance of aromatic
esters and our continuous interests on C−H carbonylation, we
wonder whether alkyl chloroformates could be used as
esterification reagents for the divergent synthesis of aromatic
65 esters. Herein, we report the Pd-catalyzed alkoxycarbonylation of
aromatic C−H bonds with chloroformates.
A variety of
benzamides and alkyl chloroformates are compatible with this
protocol, providing the access of diverse aromatic esters. The 8-
aminoquinoline (AQ) directing group[21] can be readily removed to
70 afford substituted phthalic acid esters (PAEs), 1,2-dibenzyl
alcohols and phthalamides (Scheme 1). Furthermore, besides
alkoxycarbonylation of the β-C(sp2)−H bonds, γ-C(sp2)−H
alkoxycarbonylation via a six-membered palladacycle could also
be achieved.
CO2R
R1
CO2R
O
phthalic acid esters (PAEs)
O
H
Q
Q
Pd(II)
N
OH
N
R1
R1
R1
H
H
ClCO2R2
OH
In 2008, Yu and co-workers reported the first palladium-
catalyzed oxidative ethoxycarbonylation of aromatic C–H bonds
with diethyl azodicarboxylate (DEAD).[10] Later on, the You group
40 achieved the Pd(II)-catalyzed ortho-C–H ethoxycarbonylation of
anilides with DEAD at ambient temperature.[11] Wang and co-
CO2R2
Q = 8-quinolinyl
1,2-dibenzyl alcohols
CO2NH2
ClCO2R2: readily available, operationally simple reagent
gram-scale synthesis
R1
CO2NH2
divergent synthesis of substituted PAEs,1,2-dibenzyl alcohols
and phthalamides
phthalamides
75
workers
demonstrated
a
Pd-catalyzed
ortho-C−H
Scheme 1. Pd-catalyzed C–H alkoxycarboxylation of benzamides
ethoxycarboxylation of azobenzenes and azoxybenzenes with
DEAD.[12] Besides DEAD, other regents, such as glyoxylate,[13] α-
45 keto esters,[14] di-tert-butyl decarbonate (Boc2O),[15] potassium
oxalate[16], diaziridinone,[17] and formates[18] have also been used in
the direct alkoxycarboxylation of inert C−H bonds to access esters.
Although these elegant work have significantly extend the scope
with alkyl chloroformates
We initiated our study by investigating the reaction of benamide
1a with ClCO2Et 2a. To our delight, the desired
80 ethoxycarbonylation product 3a was obtained in 72% yield in the
presence of 10% mol Pd(OAc)2, 2.0 equiv Ag2CO3 in DCE at
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100 °C for 8 h (Table 1, entry 1). The structure of 3a was 40 meta-methyl benzamide 1g exclusively gave 3g in 77% yield,
unambiguously determined by X-ray crystallography.[23] The
efficiency of the reaction was significantly affected by different
solvents. Further screening of various solvents disclosed that
toluene was the optimal for this reaction (entry 12). Other solvents
likely due to the steric interactions. When unsubstituted benzamide
View Article Online
1h and para-substituted benzamides (1i-1s) were applied as
DOI: 10.1039/C8CC06663A
substrates, the diethoxycarbonylated products were obtained (3h-
3s). It it worth noting that a broad range of synthetically useful
5
totally inhibited the reaction (entries 2-7). It should be noted that 45 functional groups, such as fluoro, trifluoromethyl, chloro, methoxy,
the alkoxycarbonylation reaction was quite sensitive to the amount
of Ag2CO3. Attempts to lower the loading of Ag2CO3 led to
reduced yield (entry 13, 42% yield) and no desired product was
bromo, iodo, acetyl, and methoxycarbonyl, were all tolerated.
Furthermore, thiophene-3-carboxamide (1t), thiophene-2-
carboxamide (1u), and benzothiophene-2-carboxamide (1v), also
reacted efficeintly with 2a to give the derired ethoxycarbonylation
10 observed in the absence of Ag2CO3 (entry 14). Other organic and
inorganic oxidants didn’t give satisfactory yields (see Table S2 for 50 products. 2-Naphthamide 1w was also viable, albeit with moderate
details). The reaction could also be conducted under air, albeit with
lower yield (entry 15, 76% yield). We further tested other
commonly used bidentate directing groups (DGs) (see Table S3 for
15 details). No reaction occurred when 2-pyridinylisopropyl (PIP)[22a]
yield (3w, 51%). When 1-naphthamide 1x was used, the desired
ethoxycarbonylation product could slowly convert to the
corresponding N-quinolinylpthalimide 3x during the column
purification.
Therefore,
a
two-step
sequence
with
and 4-amino-2,1,3-benzothiadiazole (ABTD)[22b] were used as DG. 55 alkoxycarbonyaltion/acidification was carried out and 3x was
2-Aminomethylpyridine[22c]
led
exclusively
to
the
obtained in 86% yield.
alkoxycarbonylation of amide, whereas the use of 2-
methylthioaniline[22d] gave moderate yield (31%) together with the
20 alkoxycarbonylation of amide (33%).
Table 2. Scope of benzamidesa
Table 1 Optimization of the Reaction conditionsa
aReaction conditions: 1a (0.15 mmol), 2a (3.0 equiv), Pd(OAc)2 (10 mol%),
o
Ag2CO3 (0.3 mmol) in 2.0 mL solvent at 100 C under N2 for 8 h. Yields
25 were determined by 1H NMR using CH2Br2 as the internal standard.
bIsolated yield. c1.0 equiv. Ag2CO3 was used. dWithout Ag2CO3. Under air.
n.d. = no detected.
With the optimal reaction conditions in hand, the scope of the
reaction of benzamides with ClCO2Et 2a was explored. As shown
30 in Table 2, benzamides bearing both electron-withdrawing and
electron-donating groups on the aromatic ring were well tolerated,
giving the desired products 3 in moderate to good yields. ortho-
Substituted benzamides gave mono-ethoxycarbonylation product
smoothly in good yields (3a-3d). The site selectivity was controled
35 by both electronic and steric effect, when meta-substituted
benzamides were used. For example, meta-fluoro and chloro
benzamides (1e and 1f) gave predominantly led to
ethoxycarbonylation adjacent to fluoride or chloride, due to
enhanced kinetic acidity of the corresponding C−H bonds; while
2
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a Reaction conditions: 1 (0.15 mmol), 2a (0.45 mmol, 3.0 equiv), Pd(OAc)2
Finally, a gram-scale synthesis was carried out as shown in
o
(10 mol%), Ag2CO3 (0.3 mmol) in 2.0 mL toluene at 100 C under N2 for
8 h. isolated yield. b120 oC, 12 h. Two-step procedue (see Supporting
30 Scheme 2, which showcases the robust nature of this
View Article Online
c
alkoxycarbonylation protocol. The ability to easily remove the
DOI: 10.1039/C8CC06663A
Information for details).
directing group from the final product is crucial for synthetic
applications of this reaction. Treatment of 3a with TsOH in
methanol or ethanol afforded the corresponding PAEs in good
35 yields (MeOH: 6, 76%; EtOH: 7, 75%). Notably, the 8-
aminoquinoline could be easily recovered by simple extraction.
When 3a was treated with HCl (6M), N-quinolinylpthalimide 8
was produced in 95% yield. Subsequent aminolysis gave the
phthalamide 9 in 70% yield. 1,2-Dibenzyl alcohol 3ae was
40 obtained in 62% yield with 8-aminoquinoline recovered in 58%
yield when 10 was reduced with LiBH4.
5
Next, the scope of alkyl chloroformates was investigated (Table
3). Generally, the reaction was compatible with a variety of
cloroformates. Methoxycarbonylation of benzamide 1a proceeded
smoothly to give product 4a in 73% yield under slightly modified
conditions. A number of linear alkyl chloroformates reacted with
10 1a to give the corresponding products in good yields. Interestingly,
the introduction of more sterically hindered branched-alkyl
chloroformates were also viable, affording the products in
moderate to good yields. Allyl chloroformate could also furnish
the product, albeit with a slightly lower yield (4f, 59%).
Scheme 2. Gram-scale synthesis and the removal of directing
group
15 Table 3. Scope of alkyl chloroformates.
Me
O
Me
Me
O
NH2
standard
conditions
TsOH
ROH
Q
CO2R
CO2R
Q
N
N
N
+
H
H
5 h
CO2Et
H
6, R = Me, 76%
79%
70%
3a,1.40 g, 84%
7
, R = Et, 75%
6M HCl
30 min
NH2
Me
Me
O
Me
O
N
NH3 in MeOH
OH
OH
NH2
NH2
+
Q
N
O
O
58%
10, 62%
8, 95%
9, 70%
45
In summary, we have developed a new protocol for direct
alkoxycarbonylation of β-C(sp2)−H bonds of benamides and γ-
C(sp2)−H bonds of 2-phenylacetamides. This esterification
reaction employs readily available and easily handled alkyl
50 chloroformates as etherification reagent. A variety functional
groups are tolerated. The reaction is scalable and the direct group
could be readily removed to access substituted phthalic acid esters
(PAEs), 1,2-dibenzyl alcohols and phthalamides.
55 Acknowledgements
Financial support from the NSFC (21572201, 21772170), the
National Basic Research Program of China (2015CB856600), and
Zhejiang Provincial NSFC (LR17B020001), and the Fundamental
Research Funds for the Central Universities (2018XZZX001-02)
60 is gratefully acknowledged.
aReaction conditions: 1 (0.15 mmol), Pd(OAc)2 (10 mol%), Ag2CO3 (2.0
equiv.), ClCO2R (3.0 equiv.), toluene (2 mL), 100 oC, N2, 8 h. Isolated yield.
b120 oC,12 h.
20
Alkoxycarbonylation of γ-C(sp2)−H of 2-phenylacetamides is
also possible, affording the desired product 5 in 45% yield under
slightly modified reaction conditions (eq 1, Pd(TFA)2 as catalyst).
However, satifactory conversions could only be afforded with α-
25 substituted 2-phenylacetamides. It is noteworthy that this reaction
proceeds via a six-membered palladacycle.
Notes and references
a Department of Chemistry, Zhejiang University, Hangzhou 310027, China.
E-mail: bfshi@zju.edu.cn
b
School of Chemical & Environmental Engineering, Wuyi University,
65 Jiangmen, 529020, China
† Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/b000000x/
1
2
3
R. C. Larock, Comprehensive Organic Transformations: A Guide to
Functional Group Preparations, John Wiley & Sons, New York, 1999.
J. Otera, Esterification: Methods, Reactions, and Applications, Wiley-
VCH, Weinheim, 2003.
70
For selected recent reviews on C–H activation, see: (a) R. Jazzar, J.
Hitce, A. Renaudat, J. Sofack-Kreutzer, O. Baudoin, Chem. - Eur. J.
2010, 16, 2654; (b) T. W. Lyons, M. S. Sanford, Chem. Rev. 2010,
75
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 3

ChemComm
Page 4 of 5
110, 1147; (c) D. A. Colby, R. G. Bergman, J. A. Ellman, Chem. Rev.
1830; (c) H. Li, G.-X. Cai and Z.-J. Shi, Dalton Trans., 2010, 39,
2010, 110, 624; (d) I. A. I. Mkhalid, J. H. Barnard, T. B. Marder, J.
M. Murphy, J. F. Hartwig, Chem. Rev. 2010, 110, 890; (e) C. S.
Yeung, V. M. Dong, Chem. Rev. 2011, 111, 1215; (f) M. Zhou, R. H.
Crabtree, Chem. Soc. Rev. 2011, 40, 1875; (g) S. H. Cho, J. Y. Kim,
J. Kwak, S. Chang, Chem. Soc. Rev. 2011, 40, 5068; (h) N. Kuhl, M.
N. Hopkinson, J. Wencel-Delord, F. Glorius, Angew. Chem. Int. Ed.
2012, 51, 10236; (i) G. Song, F. Wang and X. Li, Chem. Soc. Rev.,
2012, 41, 3651; (j) L. Ackermann, Acc. Chem. Res. 2014, 47, 281; (k)
10442; (d) Y. Lu, D. Leow, X. Wang, K. M. Engle and J.-Q. Yu,
Chem. Sci., 2011, 2, 967; (e) B. Liu, H.-Z. Jiang, B.-VFie.wSAhrit,icOlerOgn.line
DOI: 10.1039/C8CC06663A
Biomol. Chem. 2014, 12, 2538; (f) M. Chen, Z.-H. Ren, Y.-Y. Wang
and Z.-H. Guan, J. Org. Chem. 2015, 80, 1258; (g) Y. Wang and V.
Gevorgyan, Angew. Chem. Int. Ed. 2017, 56, 3191;
5
65
9
CO2: (a) H. Mizuno, J. Takaya and N. Iwasawa, J. Am. Chem. Soc.
2011, 133, 1251; (b) K. Sasano, J. Takaya and N. Iwasawa, J. Am.
Chem. Soc. 2013, 135, 10954.
10
Z. Huang, H. N. Lim, F. Mo, M. C. Young, G. Dong, Chem. Soc. Rev. 70 10 W.-Y. Yu, W. N. Sit, K.-M. Lai, Z. Zhou, A. S. C. Chan, J. Am. Chem.
2015, 44, 7764; (l) O. Daugulis, J. Roane, L. D. Tran, Acc. Chem. Res.
2015, 48, 1053; (m) Z. Chen, B. Wang, J. Zhang, W. Yu, Z. Liu, Y.
Zhang, Org. Chem. Front. 2015, 2, 1107; (n) J. He, M. Wasa, K. S.
L. Chan, Q. Shao, J.-Q. Yu Chem. Rev., 2017, 117, 8754.
Soc. 2008, 130, 3304.
11 Y. Huang, G. Li, J. Huang, J. You, Org. Chem. Front. 2014, 1, 347.
12 N. Xu, D. Li, Y. Zhang and L. Wang, Org. Biomol. Chem., 2015, 13,
9083.
15 4
For selected recent reviews on C–H carbonylation, see: (a) Q. Liu, H. 75 13 S. Wang, Z. Yang, J. Liu, K. Xie, A. Wang, X. Chen and Z. Tan, Chem.
Zhang, A. Lei, Angew. Chem. Int. Ed. 2011, 50, 10788; (b) X.-F. Wu,
H. Neumann, ChemCatChem 2012, 4, 447; (c) X. F. Wu, H. Neumann,
M. Beller, Chem. Rev. 2013, 113, 1; (d) B. Liu, F. Hu, and B.-F. Shi,
ACS Catal., 2015, 5 , 1863. (e) J.-B. Peng, F.-P. Wu, X.-F. Wu, Chem.
Rev. 2018, DOI: 10.1021/acs.chemrev.8b00068.
Commun., 2012, 48, 9924.
14 W. Zhou, P. Li, Y. Zhang and L. Wang, Adv. Synth. Catal., 2013, 355,
2343.
15 X. Hong, H. Wang, B. Liu and B. Xu, Chem. Commun., 2014, 50,
14129
20
80
5
For selected examples on C-H carbonyaltion, see: (a) K. Orito, A.
Horibata, T. Nakamura, H. Ushito, H. Nagasaki, M. Yuguchi, S.
Yamashita, M. Tokuda, J. Am. Chem. Soc. 2004, 126, 14342; (b) B.
Haffemayer, M. Gulias, M. J. Gaunt, Chem. Sci. 2011, 2, 312; (c) Z.-
16 Z.-Y. Li and G.-W. Wang, Org. Lett., 2015, 17, 4866
17 X. Peng, Y. Zhu, T. A. Ramirez, B. Zhao and Y. Shi, Org. Lett., 2011,
13, 5244.
18 J. Wu, J. Lan, S. Guo, J. You, Org. Lett. 2014, 16, 5862.
25
30
35
40
45
H. Guan, M. Chen, Z.-H. Ren, J. Am. Chem. Soc. 2012, 134, 17490; 85 19 T. Kochi, S. Urano, H. Seki, E. Mizushima, M. Sato and F. Kakiuchi,
(d) H. Zhang, R. Shi, P. Gan, C. Liu, A. Ding, Q. Wang and A. Lei,
Angew. Chem., Int. Ed., 2012, 51, 5204; (e) S. Luo, F.-X. Luo, X.-S.
Zhang and Z.-J. Shi, Angew. Chem., Int. Ed., 2013, 52, 10598; (f) R.
Shi, L. Lu, H. Zhang, B. Chen, Y. Sha, C. Liu, A. Lei, Angew. Chem.
Int. Ed. 2013, 52, 10582; (g) L. Grigorjeva and O. Daugulis, Org.
Lett., 2014, 16, 4688; (h) D. Liang, Y. He, Q. Zhu, Org. Lett. 2014,
16, 2748; (i) X. Li, X. Li, N. Jiao, J. Am. Chem. Soc. 2015, 137, 9246;
(j) J. Chen, J.-B. Feng, K. Natte, and X.-F. Wu, Chem. Eur. J. 2015,
21, 16370; (k) T. T. Nguyen, L. Grigorjeva, O. Daugulis, Chem.
Commun., 2017, 53, 5136. (l) S. Inoue, H. Shiota, Y. Fukumoto, N.
Chatani, J. Am. Chem. Soc. 2009, 131, 6898; ( (m) E. J. Yoo, M. Masa,
J.-Q. Yu, J. Am. Chem. Soc. 2010, 132, 17378; (n) A. McNally, B.
Haffemayer, B. S. L. Collins, M. J. Gaunt, Nature 2014, 510, 129; (o)
S. Li, G. Chen, C.-G. Feng, W. Gong, J.-Q. Yu, J. Am. Chem. Soc.
J. Am. Chem. Soc., 2009, 131, 2792.
20 G. Liao, X.-S. Yin, K. Chen, Q. Zhang, S.-Q. Zhang, B.-F. Shi, Nat.
Comm. 2016, 7, 12901.
21 V. G. Zaitsev, D. Shabashov and O. Daugulis, J. Am. Chem. Soc. 2005,
127, 13154.
90
22 (a) F.-J. Chen, S. Zhao, F. Hu, K. Chen, Q. Zhang, S.-Q. Zhang and
B.-F. Shi, Chem. Sci., 2013, 4, 4187; (b) C. Reddy, N. Bisht, R.
Parella and S. A. Babu, J. Org. Chem., 2016, 81, 12143; (c) H. Shiota,
Y. Ano, Y. Aihara, Y. Fukumoto and N. Chatani, J. Am. Chem. Soc.
2011, 133, 14952; (d) D. Shabashov and O. Daugulis, J. Am. Chem.
Soc. 2010, 132, 3965.
95
23 CCDC 1497110 (3a) contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge
Crystallographic
Data
Centre
via
2014, 136, 5267; (p) P.-L. Wang, Y. Li, Y. Wu, C. Li, Q. Lan, X.-S. 100
Wang, Org. Lett. 2015, 17, 3698; (q) C. Wang, L. Zhang, C. Chen, J.
Han, Y. Yao and Y. Zhao, Chem. Sci. 2015, 6, 4610; (r) J. Calleja, D.
Pla, T. W. Gorman, V. Domingo, B. Haffemayer, M. J. Gaunt, Nat.
Chem. 2015, 7, 1009; (s) K. F. Hogg, A. Trowbridge, A. Alvarez-
Perez ´and M. J. Gaunt, Chem. Sci., 2017, 8, 8198; (t) N. Barsu, S. K.
Bolli and B. Sundararaju, Chem. Sci., 2017, 8, 2431; (u) L. Zeng, S.
Tang, D. Wang, Y. Deng, J.-L. Chen, J.-F. Lee, and A. Lei, Org. Lett.
2017, 19, 2170.
www.ccdc.cam.ac.uk/data_request/cif.
6
50
(a) R. Giri, J.-Q. Yu, J. Am. Chem. Soc. 2008, 130, 14082; (b) R. Giri,
J. K. Lam, J.-Q. Yu, J. Am. Chem. Soc. 2010, 132, 686.
7
(a) H. Zhang, D. Liu, C. Chen, C. Liu, A. Lei, Chem. Eur. J. 2011, 17,
9581; (b) H. Chen, C. Cai, X. Liu, X. Li, H. Jiang, Chem. Commun.
2011, 47, 12224; (c) R. Lang, J. Wu, L. Shi, C. Xia, F. Li, Chem.
Commun. 2011, 47, 12553; (d) R. Lang, L. Shi, D. Li, C. Xia, F. Li,
Org. Lett. 2012, 14, 4130; (e) P. Xie, Y. Xie, B. Qian, H. Zhou, C.
Xia, H. Huang, J. Am. Chem. Soc. 2012, 134, 9902.
55
8
(a) Z.-H. Guan, Z.-H. Ren, S. M. Spinella, S. Yu, Y.-M. Liang, X.
Zhang, J. Am. Chem. Soc. 2009, 131, 729; (b) C. E. Houlden, M.
Hutchby, C. D. Bailey, J. G. Ford, S. N. G. Tyler, M. R. Gagne, G. C.
́
60
Lloyd-Jones, K. I. Booker-Milburn, Angew. Chem., Int. Ed. 2009, 48,
4
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DOI: 10.1039/C8CC06663A
A
Pd(II)ꢀcatalyzed alkoxycarbonylation of benzamide βꢀCꢀH bonds and
.
2ꢀphenylacetamide γꢀCꢀH bonds with alkyl chloroformates has been reported.