Biphenyl-based diaminophosphine oxides as air-stable preligands for the nickel-catalyzed kumada-tamao-corriu coupling of deactivated aryl chlorides, fluorides, and tosylates

Article abstract of DOI:10.1002/chem.201103050

A cooperative couple: Cooperative bimetallic activation of C-F and C-O bonds gave rise to easy coupling with aryl fluorides and tosylates. Novel air- and moisture-stable diaminophosphine oxides derived from 1,1′-biphenyl-2, 2′-diamine proved to be versatile preligands for the nickel-catalyzed cross-coupling of aryl Grignard reagents with a variety of deactivated aryl chlorides, fluorides, and tosylates (see scheme). Copyright

Full text of DOI:10.1002/chem.201103050

DOI: 10.1002/chem.201103050
Biphenyl-Based Diaminophosphine Oxides as Air-Stable Preligands for the
Nickel-Catalyzed Kumada–Tamao–Corriu Coupling of Deactivated Aryl
Chlorides, Fluorides, and Tosylates
Zhong Jin,*[a] Yan-Jing Li,[a] Yong-Qiang Ma,[b] Ling-Ling Qiu,[a] and Jian-Xin Fang*[a]
Transition-metal-catalyzed cross-coupling reactions[1] of
aryl halides or pseudo-halides with organometallic reagents,
such as Grignard reagents, organozinc compounds, boronic
acids, organostannanes, and organosiloxanes, are powerful
tools for the synthesis of the biaryl motif, which is prevalent
in natural products, pharmaceuticals, chiral ligands, liquid
crystals, and macromolecular polymers. Over the last
decade, transition-metal-catalyzed cross-coupling with aryl
chlorides[2] has been elegantly achieved by using well-de-
signed ligands, such as bulky electron-rich tertiary phos-
phines,[3] N-heterocyclic carbenes (NHCs),[4] secondary phos-
perature. Recently, great progress in transition-metal-medi-
ated cross-coupling reactions using the commonly unreactive
aryl/alkenyl sulfonylates,[8a,d] carbamates,[9] carboxylates,[10]
phenolates,[11] and so on, as the coupling substrates has been
made. The present SPO ligands are also found to be very ef-
À
fective on activation of the unreactive C O bonds in the
aryl tosylates.[12]
The reactivity of the complexes generated in situ from
these diaminophosphine oxides in the nickel-catalyzed
Kumada cross-coupling reaction significantly relates to the
substituted manner on the heteroatom adjacent to phospho-
rus atom (Table 1). With diaminophosphine oxides 1, 2, and
phine oxides (SPOs),[5] and so on. Relative to the C Cl
À
À
bonds, the C F bonds are more stable and thus inert. To
3 as a preACHTNGUTRENNUlG iHCATUNGTRENgNUGN and, although conversion ratios of aryl chloride
date, only a few protocols are known for cross-coupling with
electronically deactivated aryl fluorides.[6,7] Despite the
rather expensive cost, using aryl fluorides as coupling part-
ners contributes to the fundamental conception of the reac-
tivity of the very stable bonds and is, therefore, of great im-
portance in organometallic chemistry. Herein, we report a
new class of readily accessible, air-stable SPOs derived from
1,1’-biphenyl-2,2’-diamine (Scheme 1), which show high re-
activity in the nickel-catalyzed cross-coupling of electroni-
cally deactivated aryl chlorides and fluorides at room tem-
were obviously improved relative to a control experiment
(entry 1, Table 1), up to 15% of the homocoupling products
4,4’-dimethoxybiphenyl were observed except the desired
cross-coupling products (entries 2–4, Table 1). On the con-
trary, when the sterically congested diaminophosphine
Table 1. Nickel-catalyzed Kumada coupling of 4-chloroanisole and
PhMgBr.[a]
Entry
SPO
ligand
[Ni]
Solvent
Conv.
[%][b]
1
2
3
4
5
6
7
8
–
1
2
3
4
5
6
7
8
6
6
6
6
6
6
6
6
Ni
Ni
Ni
Ni
Ni
Ni
Ni
Ni
Ni
Ni
Ni
Ni
N
THF
THF
THF
THF
THF
THF
THF
THF
44 (21)[c]
55 (28)
54 (26)
67 (49)
93 (77)
90 (64)
100 (91)
88 (75)
Scheme 1. Structures of secondary phosphine oxides (SPOs).
9
THF
Et2O
91 (84)
10
11
12
13
14
15
16
17
39 (20)[d]
98 (89)[d]
57 (33)
THF/Et2O (2:1, v/v)
THF/DME (2:1, v/v)
100 (90)[e]
98 (87)
[a] Prof. Dr. Z. Jin, Y.-J. Li, L.-L. Qiu, Prof. J.-X. Fang
State Key Laboratory and Institute of Elemento-organic Chemistry
Nankai University
NiCl2·6H2O
NiCl2
Ni
NiCO3·H2O
Ni(acac)2
THF
THF
THF
THF
THF
92 (79)[e]
21 (–)[e,f]
98 (89)[g]
Tianjin 300071 (P.R. China)
E-mail: zjin@nankai.edu.cn
fjx@nankai.edu.cn
[a] Reaction conditions: 4-chloroanisole (1 mmol), PhMgBr (1.5 mmol,
1.0 mol LÀ1 in THF), [Ni] (3 mol%), SPO ligand (3 mol%), solvent
volume (3 mL), 20 h, RT (ca. 258C). [b] GC analysis data with n-dodec-
ane as an internal standard, isolated product yields are reported in the
parentheses. [c] Without diaminophosphine oxide. [d] PhMgBr in Et2O
(1.5 mol LÀ1) was used. [e] PhMgBr (2.0 mmol) in THF was used. [f] No
coupling products were isolated. [g] 6 mol% 6 was used.
[b] Prof. Dr. Y.-Q. Ma
Department of Applied Chemistry
China Agricultural University
Beijing 100193 (P.R. China)
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201103050.
446
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Chem. Eur. J. 2012, 18, 446 – 450

COMMUNICATION
oxides 4, 5, and 6 were used (entries 5–7, Table 1), the ho-
mocoupling side reactions were greatly suppressed.
Amongst them, preACHTUNGTRENNUNGliACHUTGTNRENNUGgand 6 gave rise to an almost quantita-
result from its insolubility in THF (entry 16, Table 1). Nota-
bly, a 2:1 ratio of 6/Ni did not provide an obviously better
conversion (entry 17, Table 1), which suggested a highly
active monophosphine-coordinated nickel species was prob-
ably dominant in the catalytic process.[13]
A variety of electron-rich aryl chlorides and heteroaryl
chlorides were capable of coupling with Grignard reagents
at ambient temperature (entries 1–13, Table 2). Except for
aryl chlorides, electronically deactivated aryl fluorides could
be also coupled at room temperature using the present cata-
lytic protocol (entries 14–20, Table 2). For polychloro- and
polyfluoroarenes, polysubstituted benzenes were obtained in
excellent yields by using an excess of a Grignard reagent
(entries 10, 11, 18, and 20, Table 2). 3-Fluorobiphenyl was
selectively produced from 1,3-difluorobenzene by using the
stoichiometrical PhMgBr (entry 19, Table 2). It is notewor-
tive conversion and no homocoupling products were identi-
fied (entry 7, Table 1). In addition, N,N’-diaryl substituted
diaminophosphine oxides 7 and 8 were also found to be ef-
fective ligands in the catalytic procedure (entries 8 and 9,
Table 1). The effects of solvent on the coupling reactions
were rather important; tetrahydrofuran proved to be the
choice of solvent, whereas ethyl ether and 1,2-dimethoxy-
ethane (DME) caused an incomplete conversion (en-
tries 10–12, Table 1). Further investigation revealed that the
forms of the nickel salts were less pronounced, and hexahy-
drate and anhydrous nickel(II) chlorides afforded an equal
catalytic performance to that of Ni
ACHTUNGTNER(NNUG acac)2 (entries 13 and 14,
Table 1), whereas the low reactivity of NiCO3·H2O might
Table 2. Nickel-catalyzed cross-coupling of aryl chlorides or fluorides with ArMgBr.[a]
Entry
1
ArCl/ArF
Product
Yield
[%][b]
Entry
11
ArCl/ArF
Product
Yield
[%][b]
91
89
88[c]
2
3
12
13
86[d]
85
83[d]
4
5
92
87
14
15
87
89
6
7
8
9
93
94
84
85
16
17
18
19
88
85
92[c]
76[e]
10
97[c]
20
90[c]
[a] Reaction conditions: ArCl or ArF (1 mmol), Grignard reagent (1.5 mmol in THF), NiCl2·6H2O (3 mol%), SPO ligand 6 (3 mol%), THF (3 mL), RT,
20 h. Reaction time not optimized. [b] Isolated product yield on the average of two runs. [c] Grignard reagent (2.5 mmol) was used. [d] NiACHTUNGTRENNUNG(acac)2
(3 mol%) was used. [e] m-Terphenyl (15%) was isolated.
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447

J.-X. Fang, Z. Jin et al.
Table 3. Nickel-catalyzed cross-coupling of aryl tosylates with ArMgBr.[a]
thy that the 2- and 3-chloro in the pyridine ring exhibited
obviously different reactivity and the coupling preferred to
take place regioselectively at the 2-position of pyridine ring
(Scheme 2). Furthermore, relative to chlorobenzene, 2-chlor-
Entry
ArOTs
Product
Yield
[%][b]
1
2
89 (96)[c]
91
3
4
85
Scheme 2. Regioselective cross-coupling of 2,3-dichloropyridine with
PhMgBr.
88 (94)[c]
5
6
90 (98)[c]
opyridine is more reactive. Thereby, 2-chloropyridine could
be chemoselectively coupled with 4-methoxyphenyl magne-
sium bromide in the presence of chlorobenzene (Scheme 3).
Syntheses of sterically hindered ortho-substituted biaryls
continue to constitute a significant challenge in transition-
metal-catalyzed cross-coupling reactions.[14] The present cat-
alytic protocol was found very effective in the formation of
di- and tri-ortho-substituted biaryls (entries 8, 9, 12, and 13,
Table 2). However, due to the considerable strong repulsion,
the coupling to the most challenging tetra-ortho-substituted
biaryls was less efficient.
87
7
8
90
86
9
85
10
84 (92)[c]
[a] Reaction conditions: aryl tosylate (1 mmol), Grignard reagent
(1.5 mmol in THF), NiCl2·6H2O (3 mol%), ligand 6 (3 mol%), THF
(3 mL), 608C, 20 h. For the corresponding aryl triflates, reactions were
performed at ambient temperature (ca. 258C). Reaction time not opti-
mized. [b] Isolated product yield on the average of two runs. [c] Yield
with the corresponding triflate.
Scheme 3. Chemoselective cross-coupling of 2-chloropyridine and chloro-
benzene.
The nickel catalyst derived from diaminophosphine oxide
6 also proved applicable to electronically deactivated aryl
tosylates (Table 3, entries 1–10). For aryl triflates, coupling
reactions could be performed even at ambient temperature
or lower. The versatile catalytic potential of the Ni/6 com-
plex makes it a powerful tool for synthesis of unsymmetric
o-, m- and p-terphenyls, which are often exploited in the
design of organic electrolumi-
phine oxide 6 had different 31P chemical shifts in CDCl3
(d=19.1 ppm) and C6D6 (d=31.5 ppm), which were proba-
À À
bly related to two tautomers. The P O Mg halide salt 9 de-
rived from diaminophosphine oxide 6 and Grignard re-
agents, which were probably actual ligand, showed high cat-
alytic activity in the nickel-mediated cross-coupling of aryl
nescent (OEL) devices[15] and
liquid crystalline materials[16]
(Scheme 4).
Analysis of the 1H NMR
spectra of compounds 1–6 sug-
gests that two unequivalent N-
alkyl substituents exist in solu-
tion, probably resulting from
the chiral center on the phos-
phorus atom and two rigid N-
alkyl groups. The diaminophos- Scheme 4. Combined cross-coupling strategies for synthesis of unsymmetric m- and p-terphenyls.
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Chem. Eur. J. 2012, 18, 446 – 450

Biphenyl-Based Diaminophosphine Oxides
COMMUNICATION
chloride (Scheme 5). As a consequence, a cooperative Ni/
Mg bimetallic action mode[6a,17] was suggested for explana-
diamine (BINAM)-derived diaminophosphine oxides for
asymmetric cross-coupling,[20] are currently under investiga-
tion.
À
À
tion of the easy activation of the C F and C O bonds by
Acknowledgements
We thank The National Natural Science Foundation of China (NNSFC)
for the financial support (Nos. 21172111 and 20502012).
Keywords: aryl fluoride · aryl tosylate · cross-coupling ·
diaminophosphine oxide · nickel
[1] a) A. Littke, in Modern Arylation Methods (Ed.: L. Ackermann),
Wiley-VCH, Weinheim, 2009, pp. 25–67; b) Metal-Catalyzed Cross-
Coupling Reactions (Eds.: A. de Meijere, F. Diederich), Wiley-VCH,
Weinheim, 2004; c) Transition Metals for Organic Synthesis (Eds.:
M. Beller, C. Bolm), Wiley-VCH, Weinheim, 2004.
À
À
Scheme 5. Nickel-catalyzed cross-coupling using the P O Mg salt as
ligand.
[2] A. F. Littke, G. C. Fu, Angew. Chem. 2002, 114, 4350–4386; Angew.
Chem. Int. Ed. 2002, 41, 4176–4211.
the present diaminophosphine oxide system (Scheme 6).
The two bulky adamantyl groups in 6 were not only benefi-
cial to the reductive elimination step in the catalytic cycle,
but also accelerated the ligand-exchange process from the
coupling product to the haloarene as the first irreversible
step in the nickel-catalyzed cross-coupling reactions,[18]
which greatly improve the turnover efficiency.
[3] a) R. Martin, S. L. Buchwald, Acc. Chem. Res. 2008, 41, 1451–1473;
b) G. C. Fu, Acc. Chem. Res. 2008, 41, 1555–1564.
[4] a) S. Diez-Gonzalez, N. Marion, S. P. Nolan, Chem. Rev. 2009, 109,
3612–3676; b) N. Marion, S. P. Nolan, Acc. Chem. Res. 2008, 41,
1440–1449; c) F. E. Hahn, M. C. Jahnke, Angew. Chem. 2008, 120,
3166–3216; Angew. Chem. Int. Ed. 2008, 47, 3122–3172; d) S. Diez-
Gonzalez, S. P. Nolan, Coord. Chem. Rev. 2007, 251, 874–883;
e) E. A. B. Kantchev, C. J. OꢁBrien, M. G. Organ, Angew. Chem.
2007, 119, 2824–2870; Angew. Chem. Int. Ed. 2007, 46, 2768–2813.
[5] a) L. Ackermann, A. Althammer, Chem. Unserer Zeit 2009, 43, 74–
83; b) L. Ackermann, Synthesis 2006, 1557–1571; c) L. Ackermann,
R. Born, J. H. Spatz, A. Althammer, C. J. Gschrei, Pure Appl.
Chem. 2006, 78, 209–214.
[6] a) N. Yoshikai, H. Matsuda, E. Nakamura, J. Am. Chem. Soc. 2009,
131, 9590–9599; b) B. T. Guan, S.-K. Xiang, T. Xu, Z.-P. Sun, B.-Q.
Wang, K.-Q. Zhao, Z.-J. Shi, Chem. Commun. 2008, 1437–1439;
c) H. Guo, F. Kong, K. Kanno, J. He, K. Nakajima, T. Takahashi, Or-
ganometallics 2006, 25, 2045–2048; d) N. Yoshikai, H. Mashima, E.
Nakamura, J. Am. Chem. Soc. 2005, 127, 17978–17979; e) L. Acker-
mann, R. Born, J. H. Spatz, D. Meyer, Angew. Chem. 2005, 117,
7382–7386; Angew. Chem. Int. Ed. 2005, 44, 7216–7219; f) J. W.
Dankwardt, J. Organomet. Chem. 2005, 690, 932–938; g) K. Lamm,
M. Stollenz, M. Meier, H. Gorls, D. Walther, J. Organomet. Chem.
2003, 681, 24–36; h) V. P. W. Bçhm, C. W. K. Gstottmayr, T. We-
skamp, W. A. Herrmann, Angew. Chem. 2001, 113, 3500–3503;
Angew. Chem. Int. Ed. 2001, 40, 3387–3389; i) Y. Kiso, K. Tamao,
M. Kumada, J. Organomet. Chem. 1973, 50, C12–C14.
À
Scheme 6. Cooperative action modes of oxidative addition toward the C
À
F and C O bonds.
[7] For cross-coupling with electron-deficient ArF or (het)ArF, see:
a) L. Ackermann, C. Wechsler, A. R. Kapdi, A. Althammer, Synthe-
sis 2010, 294–298; b) K. Inamoto, J. Kuroda, T. Sakamoto, K.
Hiroya, Synthesis 2007, 2853–2861; c) T. Wang, B. J. Alfonso, J. A.
Love, Org. Lett. 2007, 9, 5629–5631; d) T. Schaub, M. Backes, U.
Radius, J. Am. Chem. Soc. 2006, 128, 15964–15965; e) T. J. Korn,
M. A. Schade, S. Wirth, P. Knochel, Org. Lett. 2006, 8, 725–728; f) S.
Bahmanyar, S. Bahmanyar, Org. Lett. 2005, 7, 1011–1014; g) T.
Saeki, Y. Takashima, K. Tamao, Synlett 2005, 1771–1774; h) Y. M.
Kim, S. Yu, J. Am. Chem. Soc. 2003, 125, 1696–1697; i) D. A. Wid-
dowson, R. Wilhelm, Chem. Commun. 2003, 578–579; j) F. Mongin,
B. Mojovic, B. Guillamet, F. Treꢁcourt, G. Queꢁguiner, J. Org. Chem.
2002, 67, 8991–8994; k) R. Wilhelm, D. A. Widdowson, J. Chem.
Soc. Perkin Trans. 1 2000, 3808–3814; l) D. A. Widdowson, R. Wil-
helm, Chem. Commun. 1999, 2211–2213.
In summary, we have developed a new class of air-stable
diaminophosphine oxides from the commercially available
1,1’-biphenyl-2,2’-diamine. The nickel complex of the steri-
cally encumbered diaminophosphine oxide 6 exhibited supe-
rior reactivity in the cross-coupling of electronically deacti-
vated aryl chlorides, fluorides, and tosylates with Grignard
reagents. As far as we know, the catalytic system that is si-
À
À
multaneously effective for the activation of the C Cl, C F,
[19]
À
and C O bonds is rare.
The present catalytic protocol
also provides convenient access to sterically crowded di- and
tri-ortho-substituted biaryls as well as unsymmetric o-, m-
and p-terphenyls. Further applications of this type of air-
stable diaminophosphine oxides for catalysis, as well as de-
velopment of the corresponding chiral 1,1’-binaphthyl-2,2’-
[8] For selected examples, see: a) L. Ackermann, A. R. Kapdi, S.
Fenner, C. Kornhaab, C. Schulzke, Chem. Eur. J. 2011, 17, 2965–
2971; b) B.-T. Guan, X.-Y. Lu, Y. Zheng, D.-G. Yu, T. Wu, K.-L. Li,
Chem. Eur. J. 2012, 18, 446 – 450
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
449

J.-X. Fang, Z. Jin et al.
B.-J. Li, Z.-J. Shi, Org. Lett. 2010, 12, 396–399; c) T. M. Gogsig,
A. T. Lindhardt, T. Skrydstrup, Org. Lett. 2009, 11, 4886–4888; d) L.
Ackermann, A. Althammer, Org. Lett. 2006, 8, 3457–3460; e) Z.-Y.
Tang, Q.-S. Hu, J. Am. Chem. Soc. 2004, 126, 3058–3059; f) A.
Fꢂrstner, A. Leitner, Angew. Chem. 2002, 114, 632–635; Angew.
Chem. Int. Ed. 2002, 41, 609–612; g) D. Zim, V. R. Lando, J.
Dupont, A. L. Monteiro, Org. Lett. 2001, 3, 3049–3051.
Haddad, B. Z. Lu, D. Krishnamurthy, N. K. Yee, C. H. Senanayake,
Angew. Chem. 2010, 122, 6015–6019; Angew. Chem. Int. Ed. 2010,
49, 5879–5883; b) S. Calimsiz, M. Sayah, D. Mallik, M. G. Organ,
Angew. Chem. 2010, 122, 2058–2061; Angew. Chem. Int. Ed. 2010,
49, 2014–2017; c) C. M. So, W. K. Chow, P. Y. Choy, C. P. Lau, F. Y.
Kwong, Chem. Eur. J. 2010, 16, 7996–8001; d) A. Schmidt, A.
Rahimi, Chem. Commun. 2010, 46, 2995–2997; e) M. G. Organ, S.
Calimsiz, M. Sayah, K. H. Hoi, A. J. Lough, Angew. Chem. 2009,
121, 2419–2423; Angew. Chem. Int. Ed. 2009, 48, 2383–2387; f) T.
Hoshi, I. Saitoh, T. Nakazawa, T. Suzuki, J. Sakai, H. Hagiwara, J.
Org. Chem. 2009, 74, 4013–4016.
[9] For selected examples, see: a) K. W. Quasdorf, A. Antoft-Finch, P.
Liu, A. L. Silberstein, A. Komaromi, T. Blackburn, S. D. Ramgren,
K. N. Houk, V. Snieckus, N. K. Garg, J. Am. Chem. Soc. 2011, 133,
6352–6363; b) T. Mesganaw, A. L. Silberstein, S. D. Ramgren, N. F.
Fine Nathel, X. Hong, P. Liu, N. K. Garg, Chem. Sci. 2011, 2, 1766–
1771; c) K. Huang, D.-G. Yu, S.-F. Zheng, Z.-H. Wu, Z.-J. Shi,
Chem. Eur. J. 2011, 17, 786–789; d) L. Xu, B.-J. Li, Z.-H. Wu, X.-Y.
Lu, B.-T. Guan, B.-Q. Wang, K.-Q. Zhao, Z.-J. Shi, Org. Lett. 2010,
12, 884–887; e) K. W. Quasdorf, M. Riener, K. V. Petrova, N. K.
Garg, J. Am. Chem. Soc. 2009, 131, 17748–17749.
[10] For selected examples, see: a) C.-L. Sun, Y. Wang, X. Zhou, Z.-H.
Wu, B.-J. Li, B.-T. Guan, Z.-J. Shi, Chem. Eur. J. 2010, 16, 5844–
5847; b) B.-J. Li, L. Xu, Z.-H. Wu, B.-T. Guan, C.-L. Sun, B.-Q.
Wang, Z.-J. Shi, J. Am. Chem. Soc. 2009, 131, 14656–14657; c) B.-J.
Li, Y.-Z. Li, X.-Y. Lu, J. Liu, B.-T. Guan, Z.-J. Shi, Angew. Chem.
Int. Ed. 2008, 47, 10124–10127; d) B.-T. Guan, Y. Wang, B.-J. Li, D.-
G. Yu, Z.-J. Shi, J. Am. Chem. Soc. 2008, 130, 14468–14470;
e) K. W. Quasdorf, X. Tian, N. K. Garg, J. Am. Chem. Soc. 2008,
130, 14422–14423.
[15] a) P. Karastatiris, J. A. Mikroyannidis, I. K. Spiliopoulos, M. Fakis, P.
Persephonis, J. Polym. Sci. Part A, Polym. Chem. 2004, 42, 2214–
2224; b) H. Ogawa, K. Ohnishi, Y. Shirota, Synth. Met. 1997, 91,
243–245.
[16] For examples, see: a) P. Kula, R. Dabrowski, K. Kenig, D. Chyczew-
ska, Ferroelectrics 2006, 343, 19–26; b) B. Chen, U. Baumeister, G.
Pelzl, M. K. Das, X. Zeng, G. Ungar, C. Tschierske, J. Am. Chem.
Soc. 2005, 127, 16578–16591; c) A. A. Kiryanov, P. Sampson, A. J.
Seed, J. Mater. Chem. 2001, 11, 3068–3077.
[17] L. Ackermann, Isr. J. Chem. 2010, 50, 652–663.
[18] N. Yoshikai, H. Matsuda, E. Nakamura, J. Am. Chem. Soc. 2008,
130, 15258–15259.
[19] We also noted that the hydroxyphosphine ligand of Nakamura ex-
hibited high reactivity in the cross-coupling of ArF, aryl carbamates,
and phosphates with Grignard reagents (see Ref. [6a]).
[11] D.-G. Yu, Z.-J. Shi, Angew. Chem. 2011, 123, 7235–7238; Angew.
Chem. Int. Ed. 2011, 50, 7097–7100.
[20] In the preliminary experiments, using the chiral diaminophosphine
oxide derived from (R)-N,N’-di(4-biphenyl)-substituted BINAM as
[12] For recent reviews, see: a) B. M. Rosen, K. W. Quasdorf, D. A.
Wilson, N. Zhang, A. Resmerita, N. K. Garg, V. Percec, Chem. Rev.
2011, 111, 1346–1416; b) D.-G. Yu, B.-J. Li, Z.-J. Shi, Acc. Chem.
Res. 2011, 43, 1486–1495; c) B.-J. Li, D.-G. Yu, C.-L. Sun, Z.-J. Shi,
Chem. Eur. J. 2011, 17, 1728–1759.
preACTHNGURTENNUlG iAHCTUNGTRENNgUNG and, the coupling of 1-chloroisoquinoline with 2-methyl-1-
naphthyl magnesium bromide afforded the corresponding product in
85% yield with an enantiomeric excess (ee) of 17%.
[13] For a review on the monoligated transition-metal complex, see: U.
Christmann, R. Vilar, Angew. Chem. 2005, 117, 370–378; Angew.
Chem. Int. Ed. 2005, 44, 366–374.
Received: September 28, 2011
Published online: December 9, 2011
[14] For recent examples, see: a) W. Tang, A. G. Capacci, X. Wei, W. Li,
A. White, N. D. Patel, J. Savoie, J. J. Gao, S. Rodriguez, B. Qu, N.
Please note: Minor changes have been made to this publication in
Chemistry—A European Journal Early View. The Editor.
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Chem. Eur. J. 2012, 18, 446 – 450