Rhodium(I)-Catalyzed Tertiary Phosphine Directed C?H Arylation: Rapid Construction of Ligand Libraries

Article abstract of DOI:10.1002/anie.201703354

Modification of commercially available monophosphine ligands with either aryl bromides or chlorides by rhodium(I)-catalyzed, tertiary phosphine directed C?H activation is described. A series of ligand libraries containing mono- and diaryl-substituted groups, having different steric and electronic properties, were obtained in high yields. Based on the outstanding properties of their parent scaffolds, the modified ligands have been found to be powerful in organic reactions.

Full text of DOI:10.1002/anie.201703354

Angewandte
Communications
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International Edition: DOI: 10.1002/anie.201703354
German Edition: DOI: 10.1002/ange.201703354
À
C H Activation
À
Rhodium(I)-Catalyzed Tertiary Phosphine Directed C H Arylation:
Rapid Construction of Ligand Libraries
Xiaodong Qiu+, Minyan Wang+, Yue Zhao, and Zhuangzhi Shi*
Abstract: Modification of commercially available monophos-
phine ligands with either aryl bromides or chlorides by
This research was inspired by an accidental discovery in
the stoichiometric characterization of rhodium phosphine
complexes (Figure 1a). The reaction of a [{Rh(cod)Cl}2]
À
rhodium(I)-catalyzed, tertiary phosphine directed C H acti-
vation is described. A series of ligand libraries containing
mono- and diaryl-substituted groups, having different steric
and electronic properties, were obtained in high yields. Based
on the outstanding properties of their parent scaffolds, the
modified ligands have been found to be powerful in organic
reactions.
A
dvances in transition-metal catalysis are closely related to
the development of new ligands enabling previously impos-
sible transformations. In the ever-growing catalogue of
available ligands for cross-coupling reactions, tertiary phos-
phines (PR3) remain the most widely used, because their
electronic and steric properties can be altered in a systematic
and predictable way by varying the R group(s).[1] Among
them, the elegantly designed monophosphines reported by
the groups of Buchwald,[2] Beller,[3] and Kwong[4] have been
widely applied as supporting ligands in a variety of trans-
formations, especially in palladium-catalyzed carbon–carbon
and carbon–heteroatom bond-formation reactions.
Ligand modification is a powerful approach for designing
new ligands with excellent reactivity, although it occurs
seldom and unexpectedly. As early as 2000, the group of
Hartwig found that a modified phosphine, Ar5FcP(tBu)2,
generated in situ, served as the actual supporting ligand in
À
aromatic C O bond formation catalyzed by [Pd(dba)2] and
Figure 1. Synthesis of aryl-substituted biaryl phosphines. DCM=di-
chloromethane, cod=1,5-cyclooctadiene.
FcP(tBu)2.[5] This discovery led to the development of widely
used Q-Phos ligands.[6] Recently, Buchwald et al. confirmed
that the pre-ligand AdBrettPhos underwent in situ ligand
modification by dearomatization and arylation during the
palladium-catalyzed fluorination of aryl triflates.[7] This dis-
covery resulted in the design of a new ligand, AlPhos, which
allowed a highly efficient fluorination process.[8] Herein, we
report a general method for modification of commercially
dimer with CyJohnPhos (1a) in DCM at room temperature
generated a yellow complex, [Rh(cod)(CyJohnPhos)Cl] (1a’),
in 82% yield, and it was the precursor to 1a’’.[10] Treatment of
this isolated intermediate 1a’’ with 1.0 equivalent of bromo-
benzene (2a) and 3.0 equivalents of LiOtBu[11] in 1,4-dioxane
at 1108C led to the formation of the direct arylation product
3aa, which was characterized by NMR spectroscopy. It is
noted that our group and as well as that of others have
available tertiary phosphine ligands by rhodium-catalyzed, P-
atom-directed C H arylation.
[9]
À
recently reported N P(O)tBu[12]- and P(O)R2-directed[13] (e.g.
À
À
Figure 1b) C H activation reactions in which O atoms act as
[*] X. Qiu,[+] Dr. M. Wang,[+] Y. Zhao, Prof. Dr. Z. Shi
State Key Laboratory of Coordination Chemistry
School of Chemistry and Chemical Engineering
Nanjing University, Nanjing, 210093 (China)
E-mail: shiz@nju.edu.cn
Homepage: http://hysz.nju.edu.cn/zzshi/
[+] These authors contributed equally to this work.
directors for coordination with the metal centers.[14] If the P-
À
atom-directed C H arylation can be achieved in a catalytic
process,[15] this late-stage modification[16] by catalytic P-atom-
À
directed C H arylation would greatly improve the atom and
step economy for building aryl-substituted phosphine ligands,
as compared to the traditional routes (Figure 1b and c[17]).
We first established the feasibility of this proposed
transformation (Table 1). The reaction was carried out with
CyJohnPhos (1a, 1.0 equiv) and bromobenzene (2a,
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
https://doi.org/10.1002/anie.201703354.
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Table 1: Reaction development.[a]
Table 2: The scope of monoselective direct arylation.[a]
Entry [Rh] (mol%)
1a/2a Base
T
[8C]
3aa/4aa[b] Yield
[%][c]
1
2
3
4
5
6
7
8
9
[{Rh(cod)Cl}2] (100)
1:1
1:1
1:1
1:1
1:1
1:1
LiOtBu 110
LiOtBu 110
LiOtBu 110
LiOtBu 110 100:0
LiOtBu 80 100:0
KOtBu 110 100:0
95:5
99:1
99:1
94
88
86
71
52
65
72
94
80
92
–
[{Rh(cod)Cl}2] (5)
[{Rh(cod)Cl}2] (2.5)
[{Rh(cod)Cl}2] (1.5)
[{Rh(cod)Cl}2] (2.5)
[{Rh(cod)Cl}2] (2.5)
[{Rh(cod)Cl}2] (2.5)
[{Rh(cod)Cl}2] (2.5)
[Rh(PPh3)3Cl] (5)
1:2.4 LiOtBu 110
1:2.4 LiOtBu 140
1:2.4 LiOtBu 140
1:5.0 LiOtBu 150
1:2.4 LiOtBu 140
1:2.4 LiOtBu 140
15:85
1:99
1:99
1:99
–
10[d] [{Rh(cod)Cl}2] (2.5)
11
12
[Pd(dba)2] (5)
[Ir(cod)OMe]2 (5)
–
–
[a] Reaction conditions: 1a (0.20 mmol), 2a (1.0–2.4 equiv) and
3.0 equiv base in solvent at 1108C for 12 h under argon. [b] Ratios were
determined by GC. [c] Yields of the isolated major products. [d] Using
PhCl (2a’) instead of PhBr (2a). dba=dibenzylideneacetone.
1.0 equiv) in the presence of 1.0 equivalents [{Rh(cod)Cl}2]
and 3.0 equivalents LiOtBu, at 1108C under an Ar atmos-
phere in 1,4-dioxane. Gratifyingly, the desired arylation
product 3aa (mono/di = 99:1) was isolated in 94% yield
(entry 1). To our delight, a catalytic amount of [{Rh(cod)Cl}2]
(5 mol%) furnished the direct arylation product 3aa in 88%
yield (entry 2). The catalyst loading could also be further
reduced to 2.5 mol% without affecting the reactivity
(entry 3), but additional lowering to 1.5 mol% led to
decreased reactivity (entry 4). An examination of the temper-
ature revealed that a much lower yield (52%) was obtained at
808C (entry 5). Screening with another base, such as KOtBu,
confirmed LiOtBu to be the optimal additive for this reaction
(entry 6). With 2.4 equivalents of 2a, the ratio of the mono-
and disubstituted products 3aa and 4aa, respectively, was
changed to 15:85 (entry 7). To increase the di-selectivity to
a more synthetically useful level, we increased the reaction
temperature to 1408C, and it afforded 4aa in 94% yield
(entry 8). Another rhodium source, such as [Rh(PPh3)3Cl],
was also successful (entry 9). Further screening showed that
this transformation also occurred in high conversion with the
less reactive chlorobenzene (2a’) and afforded 4aa in 92%
yield (entry 10). Notably, other transition metals, such as
[Pd(dba)2][5] and [{Ir(cod)OMe}2][18] were completely ineffec-
tive in this transformation (entries 11 and 12).
[a] Reaction conditions: 2.5 mol% [{Rh(cod)Cl}2], 1 (0.20 mmol), 2
(0.20 mmol), and LiOtBu (0.6 mmol) in 1 mL 1,4-dioxane at 1108C
under argon, 24 h. Yields of products isolated after chromatography.
[b] 1.5 equiv 2, 1408C, 36 h. [c] 2.0 equiv 2, 1508C, 24 h. [d] 5.0 equiv 2,
1508C, 36 h. For X-ray structures the ellipsoids are set at 30%
probability.[23]
in forming the desired products 3da–fa in good yields.
Gratifyingly, JohnPhos (1g), having a sterically hindered
directing group, also produced the terphenyl product 3ga in
71% yield, and was prepared from 2-bromobiphenyl in three
steps with 10% total yield according to the previous route.[17a]
The cataCxium series ligands including cataCXiumꢀ PCy
(1h), POMeCy (1i), and PInCy (1j) generated the desired
biphenyl products 3ha–ja in high yields, while CM-Phos (1k)
was successfully arylated over the indole core to deliver 3ka
in 94% yield as a single regioisomer. These results reflected
the importance of the P atom as the sole director for the
regioselectivity.
The scope of the monosubstituted products was first
examined using a wide range of commercially available
phosphine ligands (Table 2). As one of the most widely used
ligands, Davephos (1b), bearing an NMe2 substituent, under-
went facile arylation to afford the corresponding product 3ba
in 87% yield. Methoxy-substitution on the substrate deliv-
ered the coupled product 3ca in 65% yield. The substrates
1d–f, containing a diphenylphosphino group, were compatible
2
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Given the importance of DavePhos, we subjected it to
tuted CyJohnphos was also developed. A number of aryl-
various arylbromides for the direct arylation process
(Table 2). Aromatic groups bearing electron-neutral and
electron-donating substituents (3bb–bf) underwent facile
transformation to afford the desired products in excellent
yields. Aryl groups with electron-withdrawing groups (3bg–
bl) could be installed on the Davephos core without any
compromise. Disubstituted arylbromides (2m–o) were effi-
ciently coupled. The naphthalene- and indole-containing
substrates 2p–q were also found tolerable. In addition,
reactivity was achieved with a very sterically hindered 9-
bromoanthracene (1r), thus providing the compound 3br in
42% yield. These results are notable because a library of aryl-
substituted Davephos analogues having different steric and
electronic properties can be generated efficiently and rapidly.
We next studied scope of the disubstituted products, and
a variety of PCy2- and PPh2-based ligands could be coupled in
excellent yields and high selectivity (Table 3). However, the
sterically hindered JohnPhos (1g), with a PtBu2 group, could
not generate the corresponding diarylation product 4ga.
Under these reaction conditions, a library of diaryl-substi-
bromides with various electronic and steric properties (4ab–
aq) could be coupled to provide the disubstituted products
with excellent selectivity. In this case, 9-bromoanthracene
(1r) only yielded the monosubstituted product (not shown in
the table). To demonstrate the efficacy of this rhodium
catalyst system, we have also prepared the compounds from
aryl chlorides such as 4aj and 4an.
À
We also sought to explore the dual C H activation of
phosphine ligands coupling with two different arylbromides
(Scheme 1). CyJohnphos (1a) was coupled with 4-bromoto-
luene (2b) under monoselective direct arylation conditions
and subsequently coupled with another arylbromide, such as
2a, 2e, 2h, 2k, and 2n in one pot to afford the desired
products in 72–83% yields.
Table 3: The scope of di-selective direct arylation.[a]
Scheme 1. One-pot synthesis of nonsymmetrical diaryl phosphines. For
X-ray structures the thermal ellipsoids are shown at 30% probability.[23]
The biaryl axially chiral monophosphine ligands play an
important role in catalytic asymmetric reactions. Aiming to
rapidly construct synthetically useful chiral ligands, we
extended this methodology to build an aryl-substituted
MOP ligand library (Table 4).[19] When (R)-H-MOP (6) was
employed, the direct arylation product (R)-Ph-MOP (7aa)
was generated in 55% yield without erosion of the ee value. A
wide range of aryl bromides bearing both electron-donating
(7ab–ae) and electron-withdrawing groups (7ag–al) proved
to be suitable coupling partners for this reaction with
acceptable yields and excellent stereochemical reliability.
Disubstituted aryl bromides (7am–ao), and 2-naphthyl bro-
mide (7ap) were also compatible with this stereospecific
process. In addition, this method also allowed direct arylation
of the P-stereogenic monophosphine 8,[20] thus affording
a bulky and stable chiral ligand 9 with excellent yield and
enantioselectivity (Scheme 2).
Finally, we tested the newly constructed ligand libraries in
two important catalytic transformations (Scheme 3). In palla-
dium-catalyzed arylation of the carboxylic ester 11, b-
arylation was predominantly observed with o-fluorobromo-
benzene (10’), whereas a-arylation was primarily observed
with m-fluorobromobenzene (10) for all ligands except with
DavePhos (1b), which gave a 47:53 mixture of the a- and b-
arylated products 12 and 13, respectively.[21] After a prelimi-
nary screening of the modified phosphine ligands in Table 2,
[a] Reaction conditions: 2.5 mol% [Rh(cod)Cl]2, 1 (0.20 mmol), 2
(0.48 mmol), and LiOtBu (0.6 mmol) in 1 mL 1,4-dioxane at 1408C
under argon, 36 h. Yields of products isolated after chromatography.
[b] 5.0 equiv ArCl (2a’), 1508C, 36 h. For X-ray structures the ellipsoids
are set at 30% probability.[23]
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Table 4: Construction of (R)-Ar-MOP library.
we found that Ph-CyJohnPhos 3aa could provide a better
result on regioselectivity (42:58). Further investigation with
the monoaryl-substituted CyJohnPhos library, 3ao was found
to be the best ligand for the b-arylated product 13 (29:71). We
also explored the developed Ar-MOP ligand library in
rhodium-catalyzed asymmetric arylation of the a,b-unsatu-
rated imine 14 with the arylstannane 15.[17b,22] Compared to
the BINAP ligand, the monodentate ligand MeO-MOP
showed good reactivity and afforded the desired product 16
in 75% yield and 88% ee. When the ligand was switched to
our modified Ar-MOP library, application of the ligand 7ao
dramatically increased the enantioselectivity to 98% with
76% yield. These examples proved the potential of the
developed ligand libraries in catalytic reactions.
In summary, a series of monophosphine ligand libraries
have been developed by rhodium(I)-catalyzed direct aryla-
tion of commercially available ligands, in which the mono-
and diselectivity can be controlled. The reaction does not
require the addition of an exogenous ligand, and is applicable
to the coupling of various aryl bromides and aryl chlorides
with the aid of the dialkyl and diaryl phosphino groups from
the parent scaffolds. Further exploration of new reactions
using these ligand libraries is ongoing in our laboratory.
[a] Reaction conditions: 5 mol% [{Rh(cod)Cl}2], 6a (0.20 mmol), 2
(2.0 mmol), and LiOtBu (0.6 mmol) in 1 mL 1,4-dioxane at 1508C under
argon, 4 days. Yields of products isolated after chromatography. For X-
ray structures the thermal ellipsoids are shown at 30% probability.[23]
Acknowledgments
We are grateful to Professor Wenjun Tang at SIOC for kindly
providing chiral ligand 8. We also thank the “1000-Youth
Talents Plan”, the “Jiangsu Specially-Appointed Professor
Plan”, NSF of China (Grant 21402086, 21401099), and NSF of
Jiangsu Province (Grant BK20140594) for financial support.
Scheme 2. Direct arylation of the ligand 8 (Tang’s ligand).
Conflict of interest
The authors declare no conflict of interest.
À
Keywords: arylation · biaryls · C H activation · P ligands ·
rhodium
[1] For a very recent example on monophosphine ligand design, see:
K. Wu, A. G. Doyle, Nat. Chem. 2017, https://doi.org/10.1002/
nchem.2741.
[2] a) P. Ruiz-Castillo, S. L. Buchwald, Chem. Rev. 2016, 116, 12564;
b) A. C. Sather, S. L. Buchwald, Acc. Chem. Res. 2016, 49, 2146.
[3] a) A. Zapf, R. Jackstell, F. Rataboul, T. Riermeier, A. Monsees,
C. Fuhrmann, N. Shaikh, U. Dingerdissen, M. Beller, Chem.
Commun. 2004, 38; b) X.-F. Wu, H. Neumann, A. Spannenberg,
T. Schulz, H. Jiao, M. Beller, J. Am. Chem. Soc. 2010, 132, 14596;
c) L. Wu, I. Fleischer, R. Jackstell, I. Profir, R. Franke, M. Beller,
J. Am. Chem. Soc. 2013, 135, 14306; d) L. Wu, I. Fleischer, R.
Jackstell, M. Beller, J. Am. Chem. Soc. 2013, 135, 3989; e) H. Li,
K. Dong, H. Jiao, H. Neumann, R. Jackstell, M. Beller, Nat.
Chem. 2016, 8, 1159.
[4] a) C. M. So, Z. Zhou, C. P. Lau, F. K. Kwong, Angew. Chem. Int.
Ed. 2008, 47, 6402; Angew. Chem. 2008, 120, 6502; b) C. M. So,
C. P. Lau, F. K. Kwong, Angew. Chem. Int. Ed. 2008, 47, 8059;
Scheme 3. Testing the developed phosphine ligand libraries.
4
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Chemie
Angew. Chem. 2008, 120, 8179; c) P. Y. Yeung, C. M. So, C. P.
Angew. Chem. Int. Ed. 2003, 42, 112; Angew. Chem. 2003, 115,
Lau, F. K. Kwong, Angew. Chem. Int. Ed. 2010, 49, 8918; Angew.
Chem. 2010, 122, 9102.
[5] a) Q. Shelby, N. Kataoka, G. Mann, J. Hartwig, J. Am. Chem.
Soc. 2000, 122, 10718; b) G. Mann, C. Incarvito, A. L. Rheingold,
J. F. Hartwig, J. Am. Chem. Soc. 1999, 121, 3224.
116; c) S. Oi, S. Watanabe, S. Fukita, Y. Inoue, Tetrahedron Lett.
2003, 44, 8665; d) R. B. Bedford, M. Betham, A. J. M. Caffyn,
J. P. H. Charmant, L. C. Lewis-Alleyne, P. D. Long, D. Polo-
Cerꢄnac, S. Prashar, Chem. Commun. 2008, 990; e) J.-F. Yang,
R.-H. Wang, Y.-X. Wang, W.-W. Yao, Q.-S. Liu, M. Ye, Angew.
Chem. Int. Ed. 2016, 55, 14116; Angew. Chem. 2016, 128, 14322.
[16] J. Wencel-Delord, F. Glorius, Nat. Chem. 2013, 5, 369.
[17] a) A. Aranyos, D. W. Old, A. Kiyomori, J. P. Wolfe, J. P. Sadighi,
S. L. Buchwald, J. Am. Chem. Soc. 1999, 121, 4369; b) T.
Hayaship, M. Ishigedani, Tetrahedron 2001, 57, 2589; c) L.
Bonnafoux, F. R. Leroux, F. Colobert, Beilstein J. Org. Chem.
2011, 7, 1278; d) M. J. Fer, J. Cinqualbre, J. Bortoluzzi, M.
Chessꢅ, F. R. Leroux, A. Panossian, Eur. J. Org. Chem. 2016,
4545.
[6] a) T. Hama, X. Liu, D. A. Culkin, J. F. Hartwig, J. Am. Chem.
Soc. 2003, 125, 11176; b) T. Hama, D. A. Culkin, J. Hartwig, J.
Am. Chem. Soc. 2006, 128, 4976; c) Y. Nakao, M. Takeda, T.
Matsumoto, T. Hiyama, Angew. Chem. Int. Ed. 2010, 49, 4447;
Angew. Chem. 2010, 122, 4549; d) S. G. Newman, J. K. Howell,
N. Nicolaus, M. Lautens, J. Am. Chem. Soc. 2011, 133, 14916;
e) S. G. Newman, M. Lautens, J. Am. Chem. Soc. 2011, 133, 1778;
f) D. A. Petrone, M. Lischka, M. Lautens, Angew. Chem. Int. Ed.
2013, 52, 10635; Angew. Chem. 2013, 125, 10829; g) Q. Li, C. W.
Liskey, J. F. Hartwig, J. Am. Chem. Soc. 2014, 136, 8755.
[7] a) D. A. Watson, M. Su, G. Teverovskiy, Y. Zhang, J. Garcꢁa-
Fortanet, T. Kinzel, S. L. Buchwald, Science 2009, 325, 1661;
b) T. J. Maimone, P. J. Milner, T. Kinzel, Y. Zhang, M. K. Takase,
S. L. Buchwald, J. Am. Chem. Soc. 2011, 133, 18106; c) H. G.
Lee, P. J. Milner, S. L. Buchwald, J. Am. Chem. Soc. 2014, 136,
3792.
À
[18] For an iridium-catalyzed phosphine-directed C H borylation,
see: K. M. Crawford, T. R. Ramseyer, C. J. A. Daley, T. B. Clark,
Angew. Chem. Int. Ed. 2014, 53, 7589; Angew. Chem. 2014, 126,
7719.
[19] a) T. Hayashi, Acc. Chem. Res. 2000, 33, 354; b) T. Hayashi, J.-W.
Han, A. Takeda, J. Tang, K. Nohmi, K. Mukaide, H. Tsuji, Y.
Uozumi, Adv. Synth. Catal. 2001, 343, 279; c) T. Shimada, Y.-H.
Cho, T. Hayashi, J. Am. Chem. Soc. 2002, 124, 13396; d) T.
Ohmura, M. Suginome, Org. Lett. 2006, 8, 2503; e) T. Ohmura,
H. Taniguchi, Y. Kondo, M. Suginome, J. Am. Chem. Soc. 2007,
129, 3518.
[8] A. C. Sather, H. G. Lee, V. Y. De La Rosa, Y. Yang, P. Mꢂller,
S. L. Buchwald, J. Am. Chem. Soc. 2015, 137, 13433.
[9] D. A. Colby, R. G. Bergman, J. A. Ellman, Chem. Rev. 2010, 110,
624.
[10] For X-ray structural characterization of 1a’’ and related
structures, see: a) A. R. OꢃConnor, W. Kaminsky, D. M. Heine-
key, K. I. Goldberg, Organometallics 2011, 30, 2105; b) Z. Liu,
H. Yamamichi, S. T. Madrahimov, J. F. Hartwig, J. Am. Chem.
Soc. 2011, 133, 2772.
[20] a) N. Hu, K. Li, Z. Wang, W. Tang, Angew. Chem. Int. Ed. 2016,
55, 5044; Angew. Chem. 2016, 128, 5128; b) W. Fu, M. Nie, A.
Wang, W. Tang, Angew. Chem. Int. Ed. 2015, 54, 2520; Angew.
Chem. 2015, 127, 2550; c) K. Du, P. Guo, Y. Chen, Z. Cao, Z.
Wang, W. Tang, Angew. Chem. Int. Ed. 2015, 54, 3033; Angew.
Chem. 2015, 127, 3076; d) C. Li, D. Chen, W. Tang, Synlett 2016,
2183.
[21] a) A. Renaudat, L. Jean-Gꢅrard, R. Jazzar, C. E. Kefalidis, E.
Clot, O. Baudoin, Angew. Chem. Int. Ed. 2010, 49, 7261; Angew.
Chem. 2010, 122, 7419; b) P. Larini, C. E. Kefalidis, R. Jazzar, A.
Renaudat, E. Clot, O. Baudoin, Chem. Eur. J. 2012, 18, 1932.
[22] a) T. Hayashi, M. Ishigedani, J. Am. Chem. Soc. 2000, 122, 976.
[23] CCDC 1548865 (1a’), 1548866 (3ba), 1548867 (3ka), 1548868
(4ja), 1548869 (4am) 1548870 (5abk), and 1548872 (7ah)
contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre.
[11] L. Ackermann, Chem. Rev. 2011, 111, 1315.
[12] a) Y. Yang, X. Qiu, Y. Zhao, Y. Mu, Z. Shi, J. Am. Chem. Soc.
2016, 138, 495; b) Y. Yang, L. R. Zhao, Y. Zhao, D. Z. Shi, J. Am.
Chem. Soc. 2016, 138, 8734.
[13] a) R.-B. Hu, H. Zhang, X.-Y. Zhang, S.-D. Yang, Chem.
Commun. 2014, 50, 2193; b) Y.-N. Ma, S.-D. Yang, Chem. Eur.
J. 2015, 21, 6673.
[14] a) H.-Y. Zhang, H.-M. Yi, G.-W. Wang, B. Yang, S.-D. Yang, Org.
Lett. 2013, 15, 6186; b) D. Zhao, C. Nimphius, M. Lindale, F.
Glorius, Org. Lett. 2013, 15, 4504; c) T. Ryu, J. Kim, Y. Park, S.
Kim, P. H. Lee, Org. Lett. 2013, 15, 3986; d) D. Gwon, D. Lee, J.
Kim, S. Park, S. Chang, Chem. Eur. J. 2014, 20, 12421; e) Y.
Unoh, T. Satoh, K. Hirano, M. Miura, ACS Catal. 2015, 5, 6634.
[15] For rhodium-mediated ortho-arylation of substituted phenol
with either phosphinite or phosphonite as a cocatalyst, see:
a) L. N. Lewis, J. F. Smith, J. Am. Chem. Soc. 1986, 108, 2728;
b) R. B. Bedford, S. J. Coles, M. B. Hursthouse, M. E. Limmert,
Manuscript received: March 31, 2017
Final Article published: && &&, &&&&
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Angewandte
Communications
Chemie
Communications
À
C H Activation
X. Qiu, M. Wang, Y. Zhao,
Z. Shi*
&&&& — &&&&
Rhodium(I)-Catalyzed Tertiary Phosphine
À
Directed C H Arylation: Rapid
Construction of Ligand Libraries
Ligand-to-ligand: A catalytic rhodium
system has been established for direct
and site-selective arylation of commer-
cially available phosphine ligands by
tion. A series of monophosphine ligand
libraries containing mono- and diaryl-
substituted groups, having different
steric and electronic properties, were
obtained in high yields.
À
tertiary phosphine directed C H activa-
6
www.angewandte.org
ꢀ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2017, 56, 1 – 6
These are not the final page numbers!