Pd-catalyzed asymmetric Suzuki–Miyaura coupling reactions for the synthesis of chiral biaryl compounds with a large steric substituent at the 2-position

Article abstract of DOI:10.3762/bjoc.16.85

Pd-catalyzed asymmetric Suzuki–Miyaura couplings of 3-methyl-2-bromophenylamides, 3-methyl-2-bromo-1-nitrobenzene and 1-naphthaleneboronic acids have been successfully developed and the corresponding axially chiral biaryl compounds were obtained in very high yields (up to 99%) with good enantioselectivities (up to 88% ee) under mild conditions. The chiral-bridged biphenyl monophosphine ligands developed by our group exhibit significant superiority to the naphthyl counterpart MOP in both reactivity and enantioselectivity control. The large steric hindrance from π-conjugated ortho-substituents of the bromobenzene substrates and the Pd···O interaction between carbonyl and palladium seem essential to achieve high enantioselectivity.

Full text of DOI:10.3762/bjoc.16.85

Pd-catalyzed asymmetric Suzuki–Miyaura coupling reactions
for the synthesis of chiral biaryl compounds with a
large steric substituent at the 2-position
Yongsu Li, Bendu Pan, Xuefeng He, Wang Xia, Yaqi Zhang, Hao Liang,
Chitreddy V. Subba Reddy, Rihui Cao and Liqin Qiu*
Full Research Paper
Open Access
Address:
Beilstein J. Org. Chem. 2020, 16, 966–973.
School of Chemistry, Guangdong Key Lab of Chiral Molecules and
Drug Discovery, Sun Yat-sen University, No. 135 Xingangxi Road,
Guangzhou 510275, People’s Republic of China
doi:10.3762/bjoc.16.85
Received: 01 March 2020
Accepted: 30 April 2020
Published: 11 May 2020
Email:
Liqin Qiu* - qiuliqin@mail.sysu.edu.cn
Dedicated to Professor Albert S. C. Chan on the occasion of his 70th
birthday.
* Corresponding author
Keywords:
Associate Editor: K. Grela
asymmetric catalysis; biaryls; monophosphine ligand; palladium
catalyst; Suzuki–Miyaura couplings
© 2020 Li et al.; licensee Beilstein-Institut.
License and terms: see end of document.
Abstract
Pd-catalyzed asymmetric Suzuki–Miyaura couplings of 3-methyl-2-bromophenylamides, 3-methyl-2-bromo-1-nitrobenzene and
1-naphthaleneboronic acids have been successfully developed and the corresponding axially chiral biaryl compounds were ob-
tained in very high yields (up to 99%) with good enantioselectivities (up to 88% ee) under mild conditions. The chiral-bridged
biphenyl monophosphine ligands developed by our group exhibit significant superiority to the naphthyl counterpart MOP in both
reactivity and enantioselectivity control. The large steric hindrance from π-conjugated ortho-substituents of the bromobenzene sub-
strates and the Pd···O interaction between carbonyl and palladium seem essential to achieve high enantioselectivity.
Introduction
Axially chiral molecules have received much attention from or Suzuki–Miyaura couplings [27-36]. In these synthetic strate-
chemists because of their widespread appearance in biological- gies, the reaction system of palladium with chiral phosphine
ly active compounds [1-4] such as vancomycin [5] and koru- ligands was studied fruitfully by Cammidge [37,38], Buchwald
pensamine A [6] and as useful chiral ligands in asymmetric ca- [13,28,39], Tang [40-43] and other groups [43-59]. Neverthe-
talysis. Different strategies with various metals and phosphine less, for the asymmetric formation of large steric systems such
ligands had been successfully employed for the efficient synthe- as sterically demanding biaryls still remain limitations [24],
sis of this scaffold [7-22], like Hiyama [23,24], Negishi [25,26] especially on how to obtain the large steric axially chiral biaryl
966

Beilstein J. Org. Chem. 2020, 16, 966–973.
with a high yield and good enantioselectivity through those cou- THF as solvent and K3PO4 as base is the most effective
pling strategies [13]. Therefore, based on our previous research combination (Table 1, entries 10–18). More results suggested
[60-65], we herein present a new method through which those that the yield varied directly proportional to the temperature,
large steric axially chiral biaryl compounds can be obtained in while the enantioselectivity went inversely (Table 1, entries
excellent yields and good enantioselectivities under mild condi- 19–21). Therefore, 50 °C was chosen as the reaction tempera-
tions, by using brominated amides and arylboronic acids as sub- ture.
strates, as well as palladium and chiral-bridged biphenyl
monophosphine ligands as catalysts.
With the optimized reaction conditions in hand, we expanded
the reaction with various functionalized starting materials, as
shown in Scheme 1. Linear N-alkyl substituted amides were
Results and Discussion
2-Bromo-3-methyl-N-phenylbenzamide (1g) and 1-naphthyl- found to produce better yields than N-branched alkyl chain
boronic acid (2a) were utilized to synthesize axially chiral com- amides, though they performed similar ee values (3a, 3b).
pound 3g. This reaction was selected as model reaction for N-Cycloalkyl-substituted amides enabled the reaction to achieve
further optimization of Pd sources, ligands (Figure 1), solvents, a quantitative conversion with good ee value (97% yield, 76%
bases and temperature. At first, various phosphine ligands were ee for 3c; 98% yield, 75% ee for 3d). The yield and ee value of
screened with 2.5 mol % Pd2(dba)3, 3.0 equivalents K3PO4 in an oxazolidinone amide were slightly lower than those of
THF at 50 °C for 72 h. The results show that the ligands have a tetrahydropyrrolamide (3e, 3f). Various aromatic substituted
large effect on the reaction. As listed in Table 1, the reaction amides were investigated. The results show that electron-rich or
was performed well and the product was obtained in 70% yield electron-deficient substituents on the phenyl ring have no sig-
when using L1 (R)-MOP as the ligand, but the enantioselectivi- nificant influence on the enantiomeric excesses of the products
ty was unsatisfactorily low (36% ee; Table 1, entry 1). After (3g–n), but the best ee value was obtained for the substrate
further examination of the ligands developed by our group with an electron-deficient phenyl ester (88% ee, 3o). By
(L2–L9), it was found that phosphine ligands with a large steric changing 1-naphthaleneboronic acid to 4-substituted-1-naph-
aryl group linked to a phosphorus atom are more effective than thaleneboronic acids 3p, 3q and 3r, the enantioselectivity and
the ligand with a cyclohexyl group both in yield and enantiose- the yield of the reaction decreased with the increase of the sub-
lectivity (Table 1, entries 2–7). The results show that the higher stituent on the boronic acid. When a methyl or methoxy group
the steric hindrance of the ligand, the better the yield and enan- were present at the ortho-position of 1-naphthaleneboronic acid,
tioselectivity. In order to find out whether the 1’-substituent of the reactions were hard to move on even at 70 °C. By replacing
the ligand has any influence on the reaction result, we replaced the 3-methyl group of the amide with a 3-methoxy or a
the methoxy group (L3) with an ethoxy group (L8), or a hydro- 3-benzyloxy group, the yield and ee value of the reaction were
gen atom (L9), which all led to a significant decrease of yield still unsatisfactory though the temperature had been raised to
and enantioselectivity (Table 1, entries 3 vs 8 and 9). Consid- 70 °C too (see Supporting Information File 1, Scheme S1, com-
ering the yield and enantioselectivity of the product comprehen- pounds 3s, 65% yield, 18% ee; 3t, 60% yield, 23% ee). In addi-
sively, L7 was chosen as the most suitable ligand for this reac- tion, phenylboric acids were also investigated, but the reaction
tion and under these conditions product 3g was obtained in 85% results were not so good (see Supporting Information File 1,
yield and with 78% ee (Table 1, entry 7). In the following Scheme S1, compounds 3u, 60% yield, 11% ee; 3v, 90% yield,
investigations, it was found that Pd2(dba)3 as palladium source, 0% ee).
Figure 1: (R)-MeO-MOP and our ligands.
967

Beilstein J. Org. Chem. 2020, 16, 966–973.
Table 1: Optimization of reaction conditionsa.
Entry
Ligand
Pd
Solvent
Base
Temp (°C)
Yield (%)b
ee (%)c
1
L1
L2
L3
L4
L5
L6
L7
L8
L9
L7
L7
L7
L7
L7
L7
L7
L7
L7
L7
L7
L7
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd(OAc)2
PdCl2
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
toluene
DME
DCE
THF
THF
THF
THF
THF
THF
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
Cs2CO3
KF
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
40
60
70
70
36
48
82
83
63
85
85
64
20
78
20
75
45
57
60
30
53
63
90
90
36
16
54
54
63
76
78
36
37
60
75
74
68
70
62
52
78
74
78
72
69
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
Pd(CF3COO)2
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
CsF
K3PO4
K3PO4
K3PO4
aReaction conditions: 1 equiv of N-aryl-bromoarylamide, 2 equiv of naphthylboronic acid, 5 mol % Pd, 6 mol % of ligand, 3 equiv of base, 2 mL sol-
vent, 50 ⁰C, 72 h. bNMR Yield. cCharacterized by HPLC with a chiral AD-H column.
More specifically, the change of the R1 group on the an amine, coupling product 5a was obtained quantitatively but
bromoamide compound has a weak influence on the coupling without any enantioselectivity. Just a slight improvement of the
reaction. No matter it was a straight alkyl chain, a branched ee value was found along with the introduction of bulkier sub-
alkyl chain, a heterocyclic group, an electron-rich aromatic or stituents to the amino group (5b–d). From the reaction results, it
an electron-deficient aromatic group, the reaction always per- can be seen that the Pd···O interaction [13,64] between the car-
formed well with high yield and good enantioselectivity. We bonyl group and the palladium plays an important role for the
guess that the large sterically hindered π-plane formed between reaction enantioselectivity. However, with the substitution of an
a carbonyl group and a benzene ring is the guarantee of high ee ester group for the amino moiety, interestingly, the situation
values of the product [13,39,42,57,65] along with the Pd···O changed significantly. The greater the ester substituent, the
interaction [13,64] between carbonyl and palladium. The exper- better the reaction results including the product yield and ee
imental results also show that the substituent of the arylboronic value. When the functional group changed from methyl ester to
acid has an obvious effect on the reaction: the yield and ee tert-butyl ester, the reaction yield rose up from 77% to 90% and
value of the product decrease with the increase of the steric the enantioselectivity increased from 35% to 70% (5e, 5f). This
hindrance of the 4-substituted boronic acid.
indicates that the O···Pd interaction between the carbonyl group
and the palladium is not strong enough to determine the enan-
Next, in order to confirm our speculation, the amide group of tioselectivity of the reaction solely, the steric hindrance from
the aryl bromide was replaced with other functional groups, as π-conjugated ortho-substituents of the bromobenzenes is also
shown in Scheme 2. When the amide group was changed into important. In addition, coupling of 2-bromo-3-nitrotoluene with
968

Beilstein J. Org. Chem. 2020, 16, 966–973.
Scheme 1: Asymmetric Suzuki–Miyaura coupling. Reaction conditions: 1 equiv N-aryl-bromoaryl compounds, 2 equiv arylboronic acids, 5 mol % Pd,
6 mol % ligand, 3 equiv of K3PO4, 2 mL THF, 50 ⁰C, 72 h; Yields are combined isolated values; ee values were determined by HPLC with chiral
columns.
969

Beilstein J. Org. Chem. 2020, 16, 966–973.
Scheme 2: Asymmetric Suzuki–Miyaura coupling. Reaction conditions: 1 equiv of bromoaryl compounds, 2 equiv of arylboronic acids, 5 mol % Pd,
6 mol % of ligand, 3 equiv of K3PO4, 2 mL THF, 50 ⁰C, 72 h; Yields are combined isolated values; ee values were determined by HPLC.
4-substituted or unsubstituted 1-naphthaleneboronic acids pro- 60% yield, 11% ee; 3v, 99% yield, 0% ee). This further demon-
vided the corresponding products in high yields with good ee strates the importance of the steric hindrance and rigidity from
values (5g, 98% yield, 75% ee; 5h, 97% yield, 83% ee; 5i, 98% the other substrate arylboronic acid. A gram-scale reaction of
yield, 85% ee) [39,62]. All these results show that the large 1h with 2a went well and provided 3h with a slightly reduced
steric hindrance from π-conjugated ortho-substituents of the yield and ee (75% yield and 73% ee, Scheme 3), compared with
bromobenzenes and the O···Pd interaction work together for the 3h in Scheme 1.
acquisition of high enantioselectivity. As stated before, the
replacement of naphthaleneboronic acid with phenylboronic According to the coordination of axial chiral phosphine ligands
acid derivatives also resulted in poor enantioselectivities of the [65,66] and our analysis, we propose a possible intermediate
products (see Supporting Information File 1, Scheme S1, 3u, structure (Scheme 4).
Scheme 3: Gram-scale reaction.
970

Beilstein J. Org. Chem. 2020, 16, 966–973.
amine (2.0 equiv) in DCM (10 mL). After that the resulting
reaction mixture was stirred for 20 h at room temperature and
checked by TLC for reaction completion. The reaction mixture
was then quenched with ice-cold water and extracted with
DCM. The organic layer was washed with brine, dried over so-
dium sulfate and concentrated under reduced pressure to obtain
the crude product. The crude product was purified by column
chromatography to obtain the desired amide compounds.
Scheme 4: Based on our analysis and speculation, a possible interme-
diate structure is proposed [65,66].
Conclusion
In summary, a Pd-catalyzed asymmetric Suzuki–Miyaura cou-
pling of 3-methyl-2-bromophenylamides or 3-methyl-2-bromo-
1-nitrobenzene and 1-naphthaleneboronic acids has been suc-
Scheme 6: Method B for the synthesis of amide substrates.
cessfully developed and the corresponding axially chiral biaryl Method B: A round bottom flask (100 mL) was charged with
compounds were obtained in very high yields (up to 99%) and 2-bromo-3-methylbenzoic acid (2.0 g, 1.0 equiv) and SOCl2
with good enantioselectivities (up to 88% ee) under mild condi- (16 mL) was added at room temperature. Then, the reaction
tions. The chiral-bridged biphenyl monophosphine ligands de- mixture was refluxed at 80 °C for 2 h. After completion of the
veloped by our group, especially L7, exhibited significant supe- reaction, the excess thionyl chloride was removed by evapora-
riority to the naphthyl counterpart MOP in reactivity and enan- tion using a rotary evaporator. Then, the corresponding
tioselectivity in the reactions. The large steric hindrance from arylamines (1.2 equiv) were added to the acyl chlorides, tri-
π-conjugated ortho-substituents of the bromobenzene sub- ethylamine (1.5 equiv) and DMAP (5 mol %) in DCM (20 mL).
strates and the existence of the O···Pd interaction between the The resulting reaction mixture was stirred for 20 h at room tem-
carbonyl group and the palladium are beneficial to acquire high perature. The completion of the reaction was monitored by
enantioselectivities.
TLC. After completion of the reaction ice-cold water was added
and the separated organic layer was washed with brine and satu-
rated sodium bicarbonate solution. Then, the organic layer was
dried over anhydrous sodium sulfate and concentrated under
reduced pressure to obtain the crude product. The crude prod-
uct was purified by column chromatography to obtain the
desired products.
Experimental
General procedure for the synthesis of amide
substrates
General procedure for the asymmetric
Suzuki–Miyaura coupling
In a glovebox, an oven-dried sealing tube (15 mL) was charged
with bromoarylamides (0.2 mmol, 1.0 equiv), Pd2(dba)3
(0.005 mmol, 5 mol % Pd), ligand L7 (0.012 mmol, 6 mol %),
arylboronic acid (0.4 mmol, 2.0 equiv), K3PO4 (0.6 mmol,
3.0 equiv) and 2 mL of dry THF. S-Phos was used as ligand for
the preparation of racemic products and all the reactions were
Scheme 5: Method A for the synthesis of amide substrates.
Method A: To a stirred solution of 2-bromo-3-methylbenzoic carried out at 50 °C for 72 h. The completion of the reaction
acid (2.0 g, 1.0 equiv) in DMF (0.05 equiv), oxalyl chloride was checked by TLC. After completion of the reaction, the
(1.5 equiv) was added in DCM (20 mL) at 0 °C. After the addi- reaction mixture was cooled to room temperature and water was
tion was completed, the reaction mixture was further stirred for added. Then, the reaction mixture was extracted with ethyl
2 h at room temperature. After the disappearance of the benzoic acetate and the organic layer was dried over anhydrous Na2SO4
acid (monitored by TLC), the corresponding arylamines and concentrated under reduced pressure to obtain the crude
(1.5 equiv) were added, followed by the addition of triethyl- product. The crude product was purified by flash chromatogra-
971

Beilstein J. Org. Chem. 2020, 16, 966–973.
14.Egami, H.; Matsumoto, K.; Oguma, T.; Kunisu, T.; Katsuki, T.
J. Am. Chem. Soc. 2010, 132, 13633–13635. doi:10.1021/ja105442m
15.Link, A.; Sparr, C. Angew. Chem., Int. Ed. 2014, 53, 5458–5461.
doi:10.1002/anie.201402441
phy using silica gel. The enantiomeric excess value of the prod-
uct was determined by HPLC by using an AD-H, OD-H or IA-3
column.
16.Chen, Y.-H.; Cheng, D.-J.; Zhang, J.; Wang, Y.; Liu, X.-Y.; Tan, B.
J. Am. Chem. Soc. 2015, 137, 15062–15065.
doi:10.1021/jacs.5b10152
Supporting Information
17.Mori, K.; Ichikawa, Y.; Kobayashi, M.; Shibata, Y.; Yamanaka, M.;
Akiyama, T. J. Am. Chem. Soc. 2013, 135, 3964–3970.
doi:10.1021/ja311902f
Supporting Information File 1
Further experimental data, copies of NMR spectra and
HPLC chromatograms.
18.Barrett, K. T.; Miller, S. J. J. Am. Chem. Soc. 2013, 135, 2963–2966.
doi:10.1021/ja400082x
[https://www.beilstein-journals.org/bjoc/content/
supplementary/1860-5397-16-85-S1.pdf]
19.Ros, A.; Estepa, B.; Ramírez-López, P.; Álvarez, E.; Fernández, R.;
Lassaletta, J. M. J. Am. Chem. Soc. 2013, 135, 15730–15733.
doi:10.1021/ja4087819
20.Bhat, V.; Wang, S.; Stoltz, B. M.; Virgil, S. C. J. Am. Chem. Soc. 2013,
135, 16829–16832. doi:10.1021/ja409383f
Funding
21.Shirakawa, S.; Wu, X.; Maruoka, K. Angew. Chem., Int. Ed. 2013, 52,
14200–14203. doi:10.1002/anie.201308237
We are grateful for financial support from the National Natural
Science Foundation of China (NSFC) (20972196, 21272283),
Guangdong Province Zhu Jiang Talents Plan (2016ZT06C090)
and Guangzhou City Talents Plan (CYLJTD-201609).
22.Shimizu, H.; Nagasaki, I.; Saito, T. Tetrahedron 2005, 61, 5405–5432.
doi:10.1016/j.tet.2005.03.022
See for a review of chiral biaryl-type bisphosphine ligands.
23.Hayashi, T.; Hayashizaki, K.; Kiyoi, T.; Ito, Y. J. Am. Chem. Soc. 1988,
110, 8153–8156. doi:10.1021/ja00232a030
ORCID® iDs
Liqin Qiu - https://orcid.org/0000-0003-1703-3530
24.Hayashi, T.; Niizuma, S.; Kamikawa, T.; Suzuki, N.; Uozumi, Y.
J. Am. Chem. Soc. 1995, 117, 9101–9102. doi:10.1021/ja00140a041
25.Genov, M.; Almorín, A.; Espinet, P. Tetrahedron: Asymmetry 2007, 18,
625–627. doi:10.1016/j.tetasy.2007.03.001
References
26.Genov, M.; Fuentes, B.; Espinet, P.; Pelaz, B. Tetrahedron: Asymmetry
2006, 17, 2593–2595. doi:10.1016/j.tetasy.2006.10.008
27.Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457–2483.
doi:10.1021/cr00039a007
1. Zehm, D.; Fudickar, W.; Hans, M.; Schilde, U.; Kelling, A.; Linker, T.
Chem. – Eur. J. 2008, 14, 11429–11441. doi:10.1002/chem.200801355
2. Clayden, J.; Moran, W. J.; Edwards, P. J.; LaPlante, S. R.
Angew. Chem., Int. Ed. 2009, 48, 6398–6401.
28.Martin, R.; Buchwald, S. L. Acc. Chem. Res. 2008, 41, 1461–1473.
doi:10.1021/ar800036s
doi:10.1002/anie.200901719
3. LaPlante, S. R.; Fader, L. D.; Fandrick, K. R.; Fandrick, D. R.;
Hucke, O.; Kemper, R.; Miller, S. P. F.; Edwards, P. J. J. Med. Chem.
2011, 54, 7005–7022. doi:10.1021/jm200584g
29.Baudoin, O. Eur. J. Org. Chem. 2005, 4223–4229.
doi:10.1002/ejoc.200500394
30.Zhang, D.; Wang, Q. Coord. Chem. Rev. 2015, 286, 1–16.
doi:10.1016/j.ccr.2014.11.011
4. Smyth, J. E.; Butler, N. M.; Keller, P. A. Nat. Prod. Rep. 2015, 32,
1562–1583. doi:10.1039/c4np00121d
31.Bringmann, G.; Walter, R.; Weirich, R. Angew. Chem., Int. Ed. Engl.
1990, 29, 977–991. doi:10.1002/anie.199009771
32.Stanforth, S. P. Tetrahedron 1998, 54, 263–303.
doi:10.1016/s0040-4020(97)10233-2
5. Hubbard, B. K.; Walsh, C. T. Angew. Chem., Int. Ed. 2003, 42,
730–765. doi:10.1002/anie.200390202
6. Watanabe, T.; Tanaka, Y.; Shoda, R.; Sakamoto, R.; Kamikawa, K.;
Uemura, M. J. Org. Chem. 2004, 69, 4152–4158.
33.Hassan, J.; Sévignon, M.; Gozzi, C.; Schulz, E.; Lemaire, M.
Chem. Rev. 2002, 102, 1359–1470. doi:10.1021/cr000664r
34.Bedford, R. B.; Cazin, C. S. J.; Holder, D. Coord. Chem. Rev. 2004,
248, 2283–2321. doi:10.1016/j.ccr.2004.06.012
doi:10.1021/jo049600x
7. Bringmann, G.; Price Mortimer, A. J.; Keller, P. A.; Gresser, M. J.;
Garner, J.; Breuning, M. Angew. Chem., Int. Ed. 2005, 44, 5384–5427.
doi:10.1002/anie.200462661
35.Denmark, S. E.; Sweis, R. F. Acc. Chem. Res. 2002, 35, 835–846.
doi:10.1021/ar020001r
8. Kozlowski, M. C.; Morgan, B. J.; Linton, E. C. Chem. Soc. Rev. 2009,
38, 3193–3207. doi:10.1039/b821092f
36.Miyaura, N.; Yamada, K.; Suzuki, A. Tetrahedron Lett. 1979, 20,
3437–3440. doi:10.1016/s0040-4039(01)95429-2
37.Cammidge, A. N.; Crépy, K. V. L. Chem. Commun. 2000, 1723–1724.
doi:10.1039/b004513f
9. Bringmann, G.; Gulder, T.; Gulder, T. A. M.; Breuning, M. Chem. Rev.
2011, 111, 563–639. doi:10.1021/cr100155e
10.Bencivenni, G. Synlett 2015, 26, 1915–1922.
doi:10.1055/s-0034-1378712
38.Cammidge, A. N.; Crépy, K. V. L. Tetrahedron 2004, 60, 4377–4386.
doi:10.1016/j.tet.2003.11.095
11.Wencel-Delord, J.; Panossian, A.; Leroux, F. R.; Colobert, F.
Chem. Soc. Rev. 2015, 44, 3418–3430. doi:10.1039/c5cs00012b
12.Uozumi, Y.; Matsuura, Y.; Arakawa, T.; Yamada, Y. M. A.
Angew. Chem., Int. Ed. 2009, 48, 2708–2710.
39.Yin, J.; Buchwald, S. L. J. Am. Chem. Soc. 2000, 122, 12051–12052.
doi:10.1021/ja005622z
40.Zhao, Q.; Li, C.; Senanayake, C. H.; Tang, W. Chem. – Eur. J. 2013,
19, 2261–2265. doi:10.1002/chem.201203898
doi:10.1002/anie.200900469
13.Shen, X.; Jones, G. O.; Watson, D. A.; Bhayana, B.; Buchwald, S. L.
J. Am. Chem. Soc. 2010, 132, 11278–11287. doi:10.1021/ja104297g
41.Li, C.; Chen, T.; Li, B.; Xiao, G.; Tang, W. Angew. Chem., Int. Ed.
2015, 54, 3792–3796. doi:10.1002/anie.201411518
972

Beilstein J. Org. Chem. 2020, 16, 966–973.
42.Tang, W.; Patel, N. D.; Xu, G.; Xu, X.; Savoie, J.; Ma, S.; Hao, M.-H.;
Keshipeddy, S.; Capacci, A. G.; Wei, X.; Zhang, Y.; Gao, J. J.; Li, W.;
Rodriguez, S.; Lu, B. Z.; Yee, N. K.; Senanayake, C. H. Org. Lett.
2012, 14, 2258–2261. doi:10.1021/ol300659d
65.Xia, W.; Zhang, Z.-W.; Li, Y.; Jiang, X.; Liang, H.; Zhang, Y.; Cao, R.;
Qiu, L. Org. Biomol. Chem. 2019, 17, 2351–2355.
doi:10.1039/c8ob03048k
66.Kim, S.-T.; Kim, S.; Baik, M.-H. Chem. Sci. 2020, 11, 1017–1025.
doi:10.1039/c9sc03095f
43.Xu, G.; Fu, W.; Liu, G.; Senanayake, C. H.; Tang, W.
J. Am. Chem. Soc. 2014, 136, 570–573. doi:10.1021/ja409669r
44.Bronger, R. P. J.; Guiry, P. J. Tetrahedron: Asymmetry 2007, 18,
1094–1102. doi:10.1016/j.tetasy.2007.04.020
45.Bermejo, A.; Ros, A.; Fernandez, R.; Lassaletta, J. M.
J. Am. Chem. Soc. 2008, 130, 15798–15799. doi:10.1021/ja8074693
46.Yamamoto, T.; Akai, Y.; Nagata, Y.; Suginome, M.
Angew. Chem., Int. Ed. 2011, 50, 8844–8847.
License and Terms
This is an Open Access article under the terms of the
Creative Commons Attribution License
doi:10.1002/anie.201103792
(http://creativecommons.org/licenses/by/4.0). Please note
that the reuse, redistribution and reproduction in particular
requires that the authors and source are credited.
47.Jensen, J. F.; Johannsen, M. Org. Lett. 2003, 5, 3025–3028.
doi:10.1021/ol034943n
48.Zhang, S.-S.; Wang, Z.-Q.; Xu, M.-H.; Lin, G.-Q. Org. Lett. 2010, 12,
5546–5549. doi:10.1021/ol102521q
49.Yang, X.; Xu, G.; Tang, W. Tetrahedron 2016, 72, 5178–5183.
doi:10.1016/j.tet.2015.12.051
The license is subject to the Beilstein Journal of Organic
Chemistry terms and conditions:
50.Ma, Y.-N.; Yang, S.-D. Chem. – Eur. J. 2015, 21, 6673–6677.
doi:10.1002/chem.201406554
(https://www.beilstein-journals.org/bjoc)
51.Ros, A.; Estepa, B.; Bermejo, A.; Álvarez, E.; Fernández, R.;
Lassaletta, J. M. J. Org. Chem. 2012, 77, 4740–4750.
doi:10.1021/jo300548z
The definitive version of this article is the electronic one
which can be found at:
52.Sawai, K.; Tatumi, R.; Nakahodo, T.; Fujihara, H.
Angew. Chem., Int. Ed. 2008, 47, 6917–6919.
doi:10.3762/bjoc.16.85
doi:10.1002/anie.200802174
53.Benhamou, L.; Besnard, C.; Kündig, E. P. Organometallics 2014, 33,
260–266. doi:10.1021/om4009982
54.Li, Y.; Tang, J.; Gu, J.; Wang, Q.; Sun, P.; Zhang, D. Organometallics
2014, 33, 876–884. doi:10.1021/om400825e
55.Wu, L.; Salvador, A.; Ou, A.; Shi, M. W.; Skelton, B. W.; Dorta, R.
Synlett 2013, 24, 1215–1220. doi:10.1055/s-0033-1338864
56.Genov, M.; Almorín, A.; Espinet, P. Chem. – Eur. J. 2006, 12,
9346–9352. doi:10.1002/chem.200600616
57.Patel, N. D.; Sieber, J. D.; Tcyrulnikov, S.; Simmons, B. J.; Rivalti, D.;
Duvvuri, K.; Zhang, Y.; Gao, D. A.; Fandrick, K. R.; Haddad, N.;
Lao, K. S.; Mangunuru, H. P. R.; Biswas, S.; Qu, B.; Grinberg, N.;
Pennino, S.; Lee, H.; Song, J. J.; Gupton, B. F.; Garg, N. K.;
Kozlowski, M. C.; Senanayake, C. H. ACS Catal. 2018, 8,
10190–10209. doi:10.1021/acscatal.8b02509
58.Uozumi, Y.; Matsuura, Y.; Suzuka, T.; Arakawa, T.; Yamada, Y. M. A.
Synthesis 2017, 49, 59–68. doi:10.1055/s-0036-1589407
59.Shen, D.; Xu, Y.; Shi, S.-L. J. Am. Chem. Soc. 2019, 141,
14938–14945. doi:10.1021/jacs.9b08578
60.Wang, S.; Li, J.; Miao, T.; Wu, W.; Li, Q.; Zhuang, Y.; Zhou, Z.; Qiu, L.
Org. Lett. 2012, 14, 1966–1969. doi:10.1021/ol300721p
61.Wu, W.; Wang, S.; Zhou, Y.; He, Y.; Zhuang, Y.; Li, L.; Wan, P.;
Wang, L.; Zhou, Z.; Qiu, L. Adv. Synth. Catal. 2012, 354, 2395–2402.
doi:10.1002/adsc.201200095
62.Zhou, Y.; Wang, S.; Wu, W.; Li, Q.; He, Y.; Zhuang, Y.; Li, L.; Pang, J.;
Zhou, Z.; Qiu, L. Org. Lett. 2013, 15, 5508–5511.
doi:10.1021/ol402666p
63.Xia, W.; Li, Y.; Zhou, Z.; Chen, H.; Liang, H.; Yu, S.; He, X.; Zhang, Y.;
Pang, J.; Zhou, Z.; Qiu, L. Adv. Synth. Catal. 2017, 359, 1656–1662.
doi:10.1002/adsc.201700020
64.Zhou, Y.; Zhang, X.; Liang, H.; Cao, Z.; Zhao, X.; He, Y.; Wang, S.;
Pang, J.; Zhou, Z.; Ke, Z.; Qiu, L. ACS Catal. 2014, 4, 1390–1397.
doi:10.1021/cs500208n
973