Selective Palladium-Catalyzed Aminocarbonylation of Olefins to Branched Amides

Article abstract of DOI:10.1002/anie.201605104

A general and efficient protocol for iso-selective aminocarbonylation of olefins with aliphatic amines has been developed for the first time. Key to the success for this process is the use of a specific 2-phosphino-substituted pyrrole ligand in the presence of PdX₂(X=halide) as a pre-catalyst. Bulk industrial and functionalized olefins react with various aliphatic amines, including amino-acid derivatives, to give the corresponding branched amides generally in good yields (up to 99 %) and regioselectivities (b/l up to 99:1).

Full text of DOI:10.1002/anie.201605104

Angewandte
Communications
Chemie
International Edition: DOI: 10.1002/anie.201605104
German Edition: DOI: 10.1002/ange.201605104
Carbonylation
Selective Palladium-Catalyzed Aminocarbonylation of Olefins to
Branched Amides
Jie Liu, Haoquan Li, Anke Spannenberg, Robert Franke, Ralf Jackstell, and Matthias Beller*
Abstract: A general and efficient protocol for iso-selective
aminocarbonylation of olefins with aliphatic amines has been
developed for the first time. Key to the success for this process is
the use of a specific 2-phosphino-substituted pyrrole ligand in
the presence of PdX2 (X = halide) as a pre-catalyst. Bulk
industrial and functionalized olefins react with various ali-
phatic amines, including amino-acid derivatives, to give the
corresponding branched amides generally in good yields (up to
99%) and regioselectivities (b/l up to 99:1).
ester (pKb = 4.87), benzylamine (pKb = 4.66), and piperidine
(pKb = 2.78) are much more basic than aniline (pKb = 9.37;
Scheme 1a).[13] Hence, aliphatic amines retard the generation
of the active palladium hydride species C, which are crucial
for catalysis (Scheme 1c). To overcome this problem, Huang
C
arbonylation reactions are widely used for the industrial
production of fine and bulk chemicals, especially to produce
valuable monomers for polymers.[1] Because of the versatility
of the carbonyl group and the possibility to easily expand
carbon chains, they also find increasing applications in
organic synthesis.[2] Within this class of reactions, transition
metal catalyzed aminocarbonylations, also called hydroami-
dations, represent a straightforward method for the conver-
sion of available olefins, CO, and amines into the correspond-
ing amides, which represent important intermediates, building
blocks, and functional molecules in organic synthesis, the
chemical industry, as well as biological systems.[3]
Since the original work of Reppe and co-workers in the
1950s,[4] numerous catalytic systems based on cobalt,[5]
nickel,[6] iron,[7] and ruthenium[8] complexes have been
developed, and allow aminocarbonylation of olefins with
amines. However, the severe reaction conditions (high
temperature and CO pressure), unavoidable byproducts
(formamide), and limited substrate scope impeded further
applications of these processes. Recently, palladium-based
catalysts for aminocarbonylation of olefins were reported
independently by the groups of Cole-Hamilton,[9] Liu,[10] and
Alper,[11] as well as our group.[12] Despite the significant
progress in this area, all these methods are limited to aromatic
amines as substrates, and carbonylations with aliphatic
amines failed. This behavior is simply explained by the
stronger basicity of aliphatic amines: For example, alanine
Scheme 1. a) The pKb of various amines. b) Two pathways for olefin
À
insertion into the Pd H bond. c) Catalytic cycle for palladium-catalyzed
branched-selective carbonylation of olefins with aliphatic amines.
and co-workers developed an elegant strategy to utilize
aminals as surrogates of aliphatic amines.[14] Alternatively, our
group applied a rhodium catalyst as the solution to this
problem.[15] Notably, both catalyst systems favor the forma-
tion of the linear amides from olefins and aliphatic amines. In
contrast, the formation of the branched amides from carbon-
ylation reactions is more challenging because of the increase
in steric effects for the olefin insertion into the palladium–
hydride bond to form the secondary carbon palladium
intermediates E (Scheme 1b).[16] Although a few examples
of branched-selective functionalization of olefins, such as
hydroformylation,[17] hydroamination,[18] hydroacylation,[19]
and hydrocyanation,[20] etc.,[16b] have been developed in
recent years, such carbonylations of aliphatic amines with
olefins, especially for industrially available bulk olefins such
as propene, hexene, octene, etc., are basically unknown and
[*] J. Liu, Dr. H. Li, Dr. A. Spannenberg, Dr. R. Jackstell, Prof. Dr. M. Beller
Leibniz-Institut fꢀr Katalyse an der Universitꢁt Rostock
Albert-Einstein-Straße 29a, 18059 Rostock (Germany)
E-mail: matthias.beller@catalysis.de
Prof. Dr. R. Franke
Evonik Industries AG
Paul-Baumann-Straße 1, 45772 Marl (Germany)
and
Lehrstuhl fꢀr Theoretische Chemie
44780 Bochum (Germany)
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
http://dx.doi.org/10.1002/anie.201605104.
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continue to be a challenging goal in homogeneous catalysis.
Herein, we report for the first time the development of
a general and efficient palladium catalyst for the amino-
carbonylation of olefins with aliphatic amines giving selec-
tively branched products.
To prevent the deactivation of the palladium hydride
catalyst by the strongly basic aliphatic amine, we investigated
the reaction of benzylamine with 1-octene (1a) in the
presence of different acidic additives including, Brønsted
acids and Lewis acids. Based on our recent work on the
alkoxylcarbonylation of olefins,[21] we used a combination of
PdCl2 and CataCXiumꢀ POMeCy (2-(dicyclohexylphos-
phino)-1-(2-methoxyphenyl)-1H-pyrrole;
L1)[22]
under
40 bar of CO in THF at 1008C. As shown in Table 1, when
Table 1: Selective aminocarbonylation of 1-octene (1a) and benzyl-
amine: Effect of additives.[a]
Entry
Additive
Yield [%]
b/l
1
2
3
4
5
6
7
8
none
0
0
0
0
0
0
0
48
–
–
–
–
–
–
–
Figure 1. Ligand effect for branched selective aminocarbonylation of
1a with 2a. Reaction conditions: 1a (2.0 mmol), 2a (1.0 mmol), PdCl2
(1.0 mol%), monodentate ligand (2.0 mol%), or bidentate ligand
(1.0 mol%), CO (40 bar), THF (2.0 mL), 1008C, 20 h. Yields and
regioselectivities were determined by GC analysis using isooctane as
the internal standard. [a] 1.5 mol% PdCl2, 3.0 mol% L2 was added,
1258C, 24 h.
NEt3·HCl (1.0 equiv)
HOAc (1.0 equiv)
HCl (10 mol%)
Zn(OTf)2 (5 mol%)
Sc(OTf)3 (5 mol%)
Yb(OTf)3 (5 mol%)
BnNH2·HCl instead of BnNH2
85:15
[a] Reaction conditions: 1a (2.0 mmol), BnNH2 (1.0 mmol), PdCl2
(1.0 mol%), ligand 1 (2.0 mol%), additive, CO (40 bar), THF (2.0 mL),
1008C, 20 h. Yields (3aa+3aa’) and regioselectivities were determined
by GC analysis using isooctane as the internal standard. Tf=trifluoro-
methanesulfonyl, THF=tetrahydrofuran.
substitution, at N on the pyrrole, from an aryl to alkyl group
(L4), did not present any improvement in this reaction.
Notably, changing the pyrrole moiety to imidazolyl and
phenyl (L5 and L6), the catalytic performance of the
corresponding catalysts declined. Interestingly, bidentate
ligands such as L7–L10 gave the linear amide as the major
product.[16a] Finally, using 1.5 mol% palladium catalyst at
1258C led to the desired product in 81% yield and good
regioselectivity (b/l = 88:12)[24] (for detailed optimization of
the reaction conditions, see the Supporting Information;
Table S1–S6.)
With the optimized reaction conditions in hand, we
explored the substrate scope. At first, the reactions of various
aliphatic amine hydrochlorides (2) with 1-octene (1a) were
studied (Table 2). With primary amines such as benzylamine
(2a), isobutylamine (2b), a-methylbenzylamine (2c), and
hexylamine (2d) as starting materials, good yields (72–80%)
and regioselectivities (b selectivity up to 88%) were achieved
(entries 1–4). More bulky substituted amines, such as isopro-
pylamine (2e) and cyclohexylamine (2 f), also underwent this
transformation smoothly in moderate to good yields (entries 5
and 6). The reaction of piperidine (2g), as an example of
a secondary amine, provided the corresponding product in
moderate yield (entry 7).
BnNH2 was used without any additives, no desired product
was observed at all (entry 1). Similarly, attempts to adjust the
pH of the reaction solution by adding hydrochloride salts, like
NEt3·HCl, did not give any product in this reaction (entry 2).
Other acidic additives, like Brønsted acids (entries 3 and 4)
and Lewis acids (entries 5–7), all turned out to be ineffective.
However, when applying BnNH2·HCl instead of BnNH2, the
branched amide (3aa) was formed with high selectivity
(85:15) albeit in moderate yield (48%) was achieved
(entry 8).
It should be noted that the observed regioselectivity is
unexpected, and it intrigued us to further investigate this
reaction. Hence, we examined the benchmark reaction in the
presence of a series of phosphines (Figure 1). When PPh3 was
used as ligand, good yield (69%) was obtained while
moderate regioselectivity was observed (b/l = 68:32). To
elaborate the influence of the ligand structure on the catalyst
reactivity, more (hetero)arylphosphine ligands were
employed (L2 to L6). To our delight, when applying L2
[2-(diphenylphosphino)-1-(2-methoxyphenyl)-1H-pyrrole]
the yield of 3aa increased to 61% with a good branched
selectivity (b/l = 88:12).[23] Notably, L3, bearing the tBu group
on phosphorus, suppressed this reaction. The modification of
Moreover, aromatic amines such as aniline were selec-
tively carbonylated to the branch amide in excellent yields
and selectivities (Table 2, entry 8). In contrast, this novel
methodology allows functionalization of a series of amino-
2
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Table 2: Palladium-catalyzed aminocarbonylation with the aliphatic
amine salts 2.[a]
methyl ester hydrochloride (2k), participated efficiently in
this process without racemization (entries 9–11). Addition-
ally, the b-amino-acid derivative b-alanine ethyl ester hydro-
chloride (2l) also reacted smoothly to give the corresponding
amide (3al) selectively (entry 12).
Next, reactions of BnNH2·HCl (2a) with bulk industrial,
as well as functionalized olefins (1), were studied. For
example, industrially important propene (1b) gave N-benzyl
isobutyric amide, in the presence of only 0.2 mol% of the
catalyst, in excellent yield (Table 3, entry 1). 1-Hexene (1c)
and 4-methyl-1-pentene (1d) also furnished the desired
aminocarbonylation products in moderate yields and
branched selectivities (entries 2 and 3). Olefins containing
Entry
1
Amine·HCl
Major product
Yield [%][b] b/l[c]
80
74
70
88:12
83:17
83:17
2
3
Table 3: Palladium-catalyzed aminocarbonylation with different olefins
(1).[a]
4
5
6
76
72
68
82:18
84:16
85:15
Entry
1[d]
Olefin
Major product
Yield [%][b]
98
b/l[c]
92:8
2
74
65
86
62
90:10
87:13
87:13
89:11
7[d]
42
82:18
3[e]
99
8[e]
87:13
91:9
(99[f])
4
9[g]
58
68
73
62
5
10[g]
11[g]
88:12
88:12
6
68
41
97
85:15
81:19
88:12
7[e]
12[g]
85:15
8
[a] Reaction conditions: 1a (2.0 mmol), 2 (1.0 mmol), PdCl2 (1.5 mol%),
L2 (3.0 mol%), CO (40 bar), THF (2.0 mL), 1258C, 24 h. [b] Yield of
isolated amides as a mixture of branched (major) and linear (minor)
products. [c] Regioselectivity was determined by GC analysis. [d] Reac-
tion at 1108C for 36 h. [e] 1a (2.0 mmol), aniline (1.0 mmol), H2O (5 mL),
PdBr2 (1.5 mol%), L2 (3.0 mol%), CO (40 bar), THF (2.0 mL), 1258C,
24 h. [f] With 1.5 mol% [Pd(L2)2Br2] pre-catalyst (complex A) as catalyst
precursor. [g] Reaction at 1258C for 36 h.
9
97
39
>99:1
10[e]
62:38
[a] Reaction conditions: 1 (2.0 mmol), 2a (1.0 mmol), PdCl2 (1.5 mol%),
L2 (3.0 mol%), CO (40 bar), THF (2.0 mL), 1258C, 24 h. [b] Yield of
isolated amides as a mixture of branched (major) and linear (minor)
products. [c] Regioselectivity was determined by GC analysis. [d] 1b
(20 mmol), 2a (5.0 mmol), PdCl2 (0.2 mol%), L2 (0.8 mol%), CO
(40 bar), THF (6.0 mL), 1308C, 36 h. [e] Reaction time of 36 h.
acid derivatives in a straightforward manner. Here, several
natural a-amino-acid derivatives, such as glycine methyl ester
(2i), l-alanine methyl ester (2j), and (S)-(+)-2-phenylglycine
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You, A. Lei, Angew. Chem. Int. Ed. 2014, 53, 2443 – 2446;
Angew. Chem. 2014, 126, 2475 – 2478; d) T. Xu, H. Alper, J. Am.
Chem. Soc. 2014, 136, 16970 – 16973; e) T. L. Andersen, S. D.
Friis, H. Audrain, P. Nordeman, G. Antoni, T. Skrydstrup, J. Am.
Chem. Soc. 2015, 137, 1548 – 1555; f) J. Cheng, X. Qi, M. Li, P.
Chen, G. Liu, J. Am. Chem. Soc. 2015, 137, 2480 – 2483; g) K. T.
Neumann, A. T. Lindhardt, B. Bang-Andersen, T. Skrydstrup,
Org. Lett. 2015, 17, 2094 – 2097; h) R. Shi, H. Zhang, L. Lu, P.
Gan, Y. Sha, H. Zhang, Q. Liu, M. Beller, A. Lei, Chem.
Commun. 2015, 51, 3247 – 3250; i) H. Yu, G. Zhang, H. Huang,
Angew. Chem. Int. Ed. 2015, 54, 10912 – 10916; Angew. Chem.
2015, 127, 11062 – 11066.
nitrile (1e), halogen (1 f), and ester groups (1g and 1h) were
efficiently converted into the branched amines (41–86%)
with good regioselectivities (entries 4–7). Allylbenzene (1i)
also demonstrated excellent reactivity and high regioselec-
tivity (entry 8). Gratifyingly, aromatic olefins like styrene (1j)
led to the corresponding amide in high yield with excellent
b selectivity (> 99%; entry 9). When (À)-b-citronellene (1k)
was used as the substrate, the internal bond remained intact
and only the double bond in the terminal position was
selectively carbonylated to the branched amide (entry 10).
In summary, we developed the first palladium catalyst
system for a general and selective aminocarbonylation of
olefins with aliphatic amines. By applying a special pyrrole-
type ligand, a wide range of aliphatic amines and olefins are
efficiently transformed into the corresponding branched
amides in good yields and often with high regioselectivity.
Apart from simple aliphatic and aromatic amines, this
procedure allows the efficient and selective aminocarbonyla-
tion of amino acids derivatives, too. In view of the easy
availability of the substrates, the efficiency, and the good
regioselectivity, this method is expected to complement the
current methods for carbonylations in organic synthesis.
[4] W. Reppe, H. Kroper, Ger. Pat. 1951, 149, 868.
[5] a) P. Pino, P. Paleari, Gazz. Chim. Ital. 1951, 81, 64; b) P. Pino, R.
Magri, Chim. Ind. 1952, 34, 511; c) S. I. Lee, S. U. Son, Y. K.
Chung, Chem. Commun. 2002, 1310 – 1311.
[6] W. Reppe, H. Main, Chem. Abstr. 1953, 47, 5428.
[7] A. Striegler, J. Weber, J. Prakt. Chem. 1965, 29, 281 – 295.
[8] Y. Tsuji, T. Ohsumi, T. Kondo, Y. Watanabe, J. Organomet.
Chem. 1986, 309, 333 – 344.
[9] C. Jimꢁnez-Rodriguez, A. A. NfflÇez-Magro, T. Seidensticker,
G. R. Eastham, M. R. L. Furst, D. J. Cole-Hamilton, Catal. Sci.
Technol. 2014, 4, 2332 – 2339.
[10] H. Liu, N. Yan, P. J. Dyson, Chem. Commun. 2014, 50, 7848 –
7851.
[11] T. Xu, F. Sha, H. Alper, J. Am. Chem. Soc. 2016, 138, 6629 – 6635.
[12] X. Fang, R. Jackstell, M. Beller, Angew. Chem. Int. Ed. 2013, 52,
14089 – 14093; Angew. Chem. 2013, 125, 14339 – 14343.
[13] a) H. K. Hall, J. Am. Chem. Soc. 1957, 79, 5441 – 5444; b) E.
Folkers, O. Runquist, J. Org. Chem. 1964, 29, 830 – 832.
[14] a) G. Zhang, B. Gao, H. Huang, Angew. Chem. Int. Ed. 2015, 54,
7657 – 7661; Angew. Chem. 2015, 127, 7767 – 7771; Vorholt and
co-workers reported a palladium-catalyzed aminocarbonylation
of aliphatic alkenes with DMF as an in situ source of CO to
produce linear amides, see: b) T. Seidensticker, M. R. L. Furst,
R. Frauenlob, J. Vondran, E. Paetzold, U. Kragl, A. J. Vorholt,
ChemCatChem 2015, 7, 4085 – 4090.
Acknowledgments
We are grateful for the financial support from Evonik
Industries AG. J.L. thanks the Chinese Scholarship Council
(CSC) for financial support (201406270115). We also thank
the analytical department in Leibniz-Institute for Catalysis at
the University of Rostock (LIKAT) for their excellent
technical and analytical support.
[15] a) K. Dong, X. Fang, R. Jackstell, G. Laurenczy, Y. Li, M. Beller,
J. Am. Chem. Soc. 2015, 137, 6053 – 6058; Behr and co-workers
reported a rhodium-catalyzed aminocarbonylation of dienes.
See: b) A. Behr, D. Levikov, E. Nurenberg, Catal. Sci. Technol.
2015, 5, 2783 – 2787.
Keywords: amines · carbonylation · olefins · P ligands ·
synthetic methodology
[16] a) G. Kiss, Chem. Rev. 2001, 101, 3435 – 3456; b) M. Beller, J.
Seayad, A. Tillack, H. Jiao, Angew. Chem. Int. Ed. 2004, 43,
3368 – 3398; Angew. Chem. 2004, 116, 3448 – 3479; c) P. Roesle,
C. J. Dürr, H. M. Mçller, L. Cavallo, L. Caporaso, S. Mecking, J.
Am. Chem. Soc. 2012, 134, 17696 – 17703; d) J. T. Christl, P.
Roesle, F. Stempfle, P. Wucher, I. Gçttker-Schnetmann, G.
Müller, S. Mecking, Chem. Eur. J. 2013, 19, 17131 – 17140.
[17] For selected examples for branched-selective hydroformylation,
see: a) N. Sakai, S. Mano, K. Nozaki, H. Takaya, J. Am. Chem.
Soc. 1993, 115, 7033 – 7034; b) M. Diꢁguez, O. Pàmies, A. Ruiz, S.
Castillón, C. Claver, Chem. Commun. 2000, 1607 – 1608; c) B.
Breit, Acc. Chem. Res. 2003, 36, 264 – 275; d) T. P. Clark, C. R.
Landis, S. L. Freed, J. Klosin, K. A. Abboud, J. Am. Chem. Soc.
2005, 127, 5040 – 5042; e) Y. Yan, X. Zhang, J. Am. Chem. Soc.
2006, 128, 7198 – 7202; f) B. Zhao, X. Peng, Z. Wang, C. Xia, K.
Ding, Chem. Eur. J. 2008, 14, 7847 – 7857; g) S. Allmendinger, H.
Kinuta, B. Breit, Adv. Synth. Catal. 2015, 357, 41 – 45; h) C. U.
Grünanger, B. Breit, Angew. Chem. Int. Ed. 2008, 47, 7346 –
7349; Angew. Chem. 2008, 120, 7456 – 7459.
[1] a) P. W. N. M. van Leeuwen, C. Claver, Rhodium Catalyzed
Hydroformylation, Vol. 22, Springer, Netherlands, 2002; b) Cat-
alytic Carbonylation Reactions (Ed.: M. Beller), Springer, Berlin
À
Heidelberg, 2006; c) B. Breit, in Metal Catalyzed Reductive C C
Bond Formation: A Departure from Preformed Organometallic
Reagents (Ed.: M. J. Krische), Springer, Berlin, Heidelberg,
2007, pp. 139 – 172; d) Modern Carbonylation Methods, Wiley-
VCH, Weinheim, 2008; e) Transition Metals for Organic Syn-
thesis: Building Blocks and Fine Chemicals (Eds.: M. Beller, C.
Bolm), Wiley-VCH, Weinheim, 2008; f) R. Franke, D. Selent, A.
Bçrner, Chem. Rev. 2012, 112, 5675 – 5732.
[2] a) Q. Liu, H. Zhang, A. Lei, Angew. Chem. Int. Ed. 2011, 50,
10788 – 10799; Angew. Chem. 2011, 123, 10978 – 10989; b) X.-F.
Wu, H. Neumann, M. Beller, Chem. Soc. Rev. 2011, 40, 4986 –
5009; c) L. Wu, X. Fang, Q. Liu, R. Jackstell, M. Beller, X.-F. Wu,
ACS Catal. 2014, 4, 2977 – 2989; d) X.-F. Wu, X. Fang, L. Wu, R.
Jackstell, H. Neumann, M. Beller, Acc. Chem. Res. 2014, 47,
1041 – 1053; e) B. Sam, B. Breit, M. J. Krische, Angew. Chem. Int.
Ed. 2015, 54, 3267 – 3274; Angew. Chem. 2015, 127, 3317 – 3325.
[3] a) P. Hermange, A. T. Lindhardt, R. H. Taaning, K. Bjerglund,
D. Lupp, T. Skrydstrup, J. Am. Chem. Soc. 2011, 133, 6061 – 6071;
b) T. Xu, H. Alper, Tetrahedron Lett. 2013, 54, 5496 – 5499; c) W.
Li, C. Liu, H. Zhang, K. Ye, G. Zhang, W. Zhang, Z. Duan, S.
[18] For selected examples for branched-selective hydroamination,
see: a) T. E. Müller, M. Beller, Chem. Rev. 1998, 98, 675 – 704;
b) J. F. Hartwig, Pure Appl. Chem. 2004, 76, 507; c) T. E. Müller,
K. C. Hultzsch, M. Yus, F. Foubelo, M. Tada, Chem. Rev. 2008,
108, 3795 – 3892; d) Y. Yang, S.-L. Shi, D. Niu, P. Liu, S. L.
Buchwald, Science 2015, 349, 62 – 66.
4
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[19] For selected examples for branched-selective hydroacylation,
[22] A. Zapf, R. Jackstell, F. Rataboul, T. Riermeier, A. Monsees, C.
see: a) R. T. Stemmler, C. Bolm, Adv. Synth. Catal. 2007, 349,
1185 – 1198; b) K. Hirano, A. T. Biju, I. Piel, F. Glorius, J. Am.
Chem. Soc. 2009, 131, 14190 – 14191; c) M. C. Willis, Chem. Rev.
2010, 110, 725 – 748; d) I. Piel, M. Steinmetz, K. Hirano, R.
Frçhlich, S. Grimme, F. Glorius, Angew. Chem. Int. Ed. 2011, 50,
4983 – 4987; Angew. Chem. 2011, 123, 5087 – 5091; e) J. C. Leung,
M. J. Krische, Chem. Sci. 2012, 3, 2202 – 2209; f) J. S. Bandar, E.
Ascic, S. L. Buchwald, J. Am. Chem. Soc. 2016, 138, 5821 – 5824;
g) L.-J. Xiao, X.-N. Fu, M.-J. Zhou, J.-H. Xie, L.-X. Wang, X.-F.
Xu, Q.-L. Zhou, J. Am. Chem. Soc. 2016, 138, 2957 – 2960.
[20] For selected examples for branched-selective hydrocyanation,
see: a) P. Arthur, D. C. England, B. C. Pratt, G. M. Whitman, J.
Am. Chem. Soc. 1954, 76, 5364 – 5367; b) C. A. Tolman, W. C.
Seidel, J. D. Druliner, P. J. Domaille, Organometallics 1984, 3,
33 – 38; c) B. Gaspar, E. M. Carreira, Angew. Chem. Int. Ed.
2007, 46, 4519 – 4522; Angew. Chem. 2007, 119, 4603 – 4606; d) L.
Bini, C. Muller, D. Vogt, Chem. Commun. 2010, 46, 8325 – 8334.
[21] H. Li, K. Dong, H. Jiao, H. Neumann, R. Jackstell, M. Beller,
Nat. Chem. 2016, DOI: 10.1038/nchem.2586.
Fuhrmann, N. Shaikh, U. Dingerdissen, M. Beller, Chem.
Commun. 2004, 38 – 39.
[23] The molecular structure of the [Pd(L2)2Br2] pre-catalyst
(CCDC 1480945) is given in supporting information (Figure S1).
CCDC 1480945 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre.
[24] Theoretically, simple 1-octene might form four different regio-
isomeric C9-amides because of the olefin isomerization reaction
and then followed by carbonylation of different internal olefins.
In the presence of our catalyst system, 3aa and 3aa’ were mainly
obtained and only trace amounts of other internal isomeric
amides were observed by GC.
Received: May 25, 2016
Published online: && &&, &&&&
Angew. Chem. Int. Ed. 2016, 55, 1 – 6
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5
These are not the final page numbers!

Angewandte
Communications
Chemie
Communications
Carbonylation
J. Liu, H. Li, A. Spannenberg, R. Franke,
R. Jackstell, M. Beller*
&&&& — &&&&
Selective Palladium-Catalyzed
Aminocarbonylation of Olefins to
Branched Amides
Branch out: A general protocol for iso-
selective olefin aminocarbonylation has
been developed. Key to success is the use
of a specific 2-phosphino-substituted
pyrrole ligand in the presence of PdX2.
Bulk industrial and functionalized olefins
react with various aliphatic amines,
including amino acid derivatives, to give
the corresponding branched amides in
good yields and regioselectivities.
6
www.angewandte.org
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2016, 55, 1 – 6
These are not the final page numbers!