Palladium-catalyzed Suzuki-Miyaura coupling of aryl sulfamates with arylboronic acids

Article abstract of DOI:10.1039/c3ob41382a

Readily available NHC-Pd(ii)-Mp complexes 2 showed efficient catalytic activity toward the Suzuki-Miyaura coupling of aryl sulfamates with arylboronic acids or potassium phenyltrifluoroborate, giving the expected coupling products in good to high yields.

Full text of DOI:10.1039/c3ob41382a

Organic &
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PAPER
Palladium-catalyzed Suzuki–Miyaura coupling of aryl
sulfamates with arylboronic acids†
Zhan-Yong Wang,a Qin-Na Ma,a Ren-Hao Lia and Li-Xiong Shao*a,b
Cite this: Org. Biomol. Chem., 2013, 11,
7899
Readily available NHC–Pd(II)–Mp complexes 2 showed efficient catalytic activity toward the Suzuki–
Miyaura coupling of aryl sulfamates with arylboronic acids or potassium phenyltrifluoroborate, giving the
expected coupling products in good to high yields. It should be noted that this is the first example so far
of the phosphine-free, NHC–Pd(II) complexes catalyzed Suzuki–Miyaura coupling of aryl sulfamates with
arylboronic acids.
Received 5th July 2013,
Accepted 19th September 2013
DOI: 10.1039/c3ob41382a
www.rsc.org/obc
progress has been achieved, reported methods are mainly
limited to Ni catalysts, which still have some drawbacks such
Introduction
Transition metal catalyzed Suzuki–Miyaura coupling is one of as relatively high catalyst loading, along with phosphine-based
the most versatile methods for the formation of carbon– ligands. Furthermore, to the best of our knowledge, at present,
carbon bonds.1 Traditionally, aryl (pseudo)halides have been no Pd-catalyzed reactions of aryl sulfamates with arylboronic
used as electrophiles. During the past few years, electrophiles acids are known. Thus, we turned our attention to the NHC–
have been extended to more challenging substrates such as C– Pd(II) complexes catalyzed Suzuki–Miyaura coupling of aryl sul-
O-based electrophiles.2 Recently, we have reported that the famates. In our further investigations, it was found that
N-heterocyclic carbene–palladium(II)-1-methylimidazole [NHC– N-heterocyclic carbene–palladium(II)–morpholine [NHC–Pd(II)–
Pd(II)–Im] complex is an efficient catalyst for the Suzuki– Mp] complexes are efficient catalysts in the Suzuki–Miyaura
Miyaura coupling of aryl sulfonates with arylboronic acids coupling of aryl sulfamates with arylboronic acids or potassium
using morpholine as the sole solvent. Further control experi- phenyltrifluoroborate. Herein, we report these results in detail.
ments showed that in the reported procedure, the imidazole
moiety in the NHC–Pd(II)–Im complex can be displaced by
morpholine, thus resulting in the N-heterocyclic carbene–
palladium(II)–morpholine [NHC–Pd(II)–Mp] complex as a real
Results and discussion
First, using our previously reported procedure,6 NHC–Pd(II)–
precatalyst, which can also display a similar catalytic activity to
that of the NHC–Pd(II)–Im complex.3 These results thus
Mp complexes 2 were easily obtained in 75–85% yield from
commercially available imidazolium salts 1, PdCl2 and mor-
pholine in a one-step process (Scheme 1). The complexes are
air-, moisture- and thermal-stable and can be kept under air at
least for several weeks.
motivated us to further investigate these complexes in the
Suzuki–Miyaura coupling using other less active, challenging
C–O-based electrophiles.
Sulfamates, which can also be easily prepared from cheap
and commercially available phenols with dimethylsulfamoyl
chloride, are also attractive electrophiles. Compared to the
transition metal complexes catalyzed coupling reactions using
aryl sulfonates as electrophiles,3 less attention has been paid
to the field of aryl sulfamates, which are more unreactive in
coupling reactions.4,5 In addition, although significant
aCollege of Chemistry and Materials Engineering, Wenzhou University, Chashan
University Town, Wenzhou, Zhejiang Province 325035, People’s Republic of China.
E-mail: Shaolix@wzu.edu.cn; Fax: +86 57786689300; Tel: +86 57786689300
bCollege of Chemistry and Life Sciences, Zhejiang Normal University, Jinhua,
Zhejiang Province 321004, People’s Republic of China
†Electronic supplementary information (ESI) available: 1H and 13C NMR spectra
of compounds 2 and 5. See DOI: 10.1039/c3ob41382a
Scheme 1 Synthesis of the NHC–Pd(II)–Mp complexes 2.
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Table 1 Optimization of the NHC–Pd(II)–Mp complexes 2 catalyzed coupling of
sulfamate 3a with 4-methoxyphenylboronic acid 4a
Table 2 NHC–Pd(II)–Mp complex 2a catalyzed coupling of sulfamate 3a with
arylboronic acid 4 under optimal conditions
Entrya
2
Base
Solvent
Yieldb (%)
Entrya
4 (R)
Yieldb (%)
1
2
3
4
5
6
7
8
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2b
2c
2a
2a
2a
2a
2a
KF·2H2O
K3PO4·3H2O
K2CO4
Na3PO4·12H2O
KHCO3
KAOc
Morpholine–H2O
Morpholine–H2O
Morpholine–H2O
Morpholine–H2O
Morpholine–H2O
Morpholine–H2O
Morpholine–H2O
Morpholine–H2O
Morpholine–H2O
Toluene–H2O
6
84
51
57
5
26
94
48
24
7
1
2
3
4
5
6
7
8
4a (4-MeO)
4b (3-MeO)
4c (2-MeO)
4d (4-Me)
4e (3-Me)
4f (2-Me)
4g (4-F)
4h (3-F)
4i (2-F)
4j (3,5-Me2)
4k (H)
5a, 94
5b, 80
5c, 30
5d, 93
5e, 88
5f, 74
5g, 84
5h, 57
5i, <5
5j, 89
5k, 85
5l, 80
Cs2CO3
KOtBu
9
NaOtBu
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
No base
9
10
11
12
13
14
15
16
17
18
19
10
11
12
DMF–H2O
Dioxane–H2O
20
5
Morpholine–H2O
Morpholine–H2O
Morpholine
72
81
60
89
83
38
ND
Morpholine–H2Oc
Morpholine–H2Od
Morpholine–H2Oe
Morpholine–H2O
13
5m, 92
a Unless otherwise specified, all reactions were carried out using 3a
(0.7 mmol), 4a (1.2 mol%), and base (3.0 equiv.) in the mixture of
organic solvent (1.0 mL) and H2O (0.1 mL) at 110 °C for 12 h.
b Isolated yields. c Morpholine–H2O = 1.0/0.2 mL. d Morpholine–H2O =
1.0/0.3 mL. e Morpholine–H2O = 1.0/0.5 mL.
a All reactions were carried out using 3a (0.7 mmol), 4 (1.2 equiv.), 2a
(2.0 mol%), and Cs2CO3 (3.0 equiv.) in the mixture of morpholine
(1.0 mL) and H2O (0.1 mL) at 110 °C for 12 h. b Isolated yields.
Under optimal conditions, the reactions between sulfamate
Subsequently, using sulfamate 3a (0.7 mmol) and 4-meth- 3a and a range of arylboronic acids 4 were first investigated
oxyphenylboronic acid 4a (1.2 equiv.) as the model coupling (Table 2). As can be seen from Table 2, most reactions pro-
partners, a mixture of morpholine and H2O (1.0 mL/0.1 mL) as ceeded well to give the corresponding coupling products 5 in
the solvent, and the NHC–Pd(II)–Mp complex 2a (2.0 mol%) as good to high yields under optimal conditions. It seems that
the catalyst, initial investigations were carried out at 110 °C for substituents on the different positions of phenyl groups of
12 h to find the most efficient base (Table 1, entries 1–9). It arylboronic acids 4 affected the reactions to some extent. For
was found that Cs2CO3 was the best base to give the expected instance, both electron-rich (MeO- and Me-) and electron-poor
coupling product 5a in 94% yield (Table 1, entry 7). The (F-) substituents on the para-position of arylboronic acids 4
solvent effect was also investigated and the mixture of morpho- gave the best yields, and those on the meta-position gave mod-
line and water was shown to be the best (Table 1, entry 7 vs. erate yields, while those on the ortho-position gave the worst
entries 10–12). Further studies showed that the NHC–Pd(II)– yields (Table 2, entries 1–3, 4–6 and 7–9). It may be attributed
Mp complex 2a showed the best catalytic activity over com- to the steric hindrance of the corresponding substituents. In
plexes 2b (72%) and 2c (81%) (Table 1, entry 7 vs. entries 13 addition, only 30% yield of product 5c was obtained for the
and 14). In addition, it was found that the water added as the reaction involving 2-methoxyphenylboronic acid 4c, probably
co-solvent had some effect on this reaction. For example, due also to the coordination of the ortho-oxygen atom to the
when morpholine alone was used as the solvent, product 5a metal center (Table 2, entry 3). Furthermore, almost no
can only be obtained in 60% yield (Table 1, entry 15). Further- product was detected when 2-fluorophenylboronic acid was
more, the yield of 5a decreased when the amount of the water used (Table 2, entry 9), which may also be attributed to its
added was increased (Table 1, entries 16–18). Therefore, it can lower reactivity in the transmetallation process.7 In these
be concluded that the mixture solvent of morpholine and cases, lower yields for fluorophenylboronic acids were found
water (1.0/0.1 mL) was the most suitable (Table 1, entry 7). when compared to the previous nickel-catalyzed reactions of
Introduction of an additional base such as Cs2CO3 was this type, maybe due mainly to the inferior catalytic activity of
also essential for this reaction, which suggests that morpho- the NHC–Pd(II)–Mp complex in such reactions.4h The reactions
line in this case cannot play the role of a suitable base involving 1-naphthylboronic acid 4l and its analogue,
(Table 1, entry 19).
2-naphthylboronic acid 4m, performed well to give products 5l
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and 5m in 80% and 92% yields, respectively (Table 2, entries
12 and 13).
Table 3 NHC–Pd(II)–Mp complex 2a catalyzed coupling of sulfamates 3a with
arylboronic acid 4 under optimal conditions
Furthermore, the scope of this reaction was next examined
with regard to functional group tolerance both on the sub-
strates 2 and on boronic acids 3 (Table 3). As can be seen from
Table 3, most reactions proceeded smoothly to give the desired
coupling products 5 in good to high yields under identical
conditions. It seems that with the combination of sulfamates 3
and arylboronic acids 4 shown in Table 3, substituents on
both substrates have almost no effect on the reactions in these
cases. Furthermore, the formyl group on the sulfamate is also
tolerated to give the corresponding coupling products 5ab and
5ac in acceptable yields, respectively (Table 3, entries 16 and
17). Moreover, heteroaryl sulfamates 3i–3m were also found to
be good partners under identical conditions to give the
desired products 5ag–5ap in good to high yields (Table 3,
entries 21–30).
During the past few years, organotrifluoroborate alkali
metal salts, which generally possess the advantages of greater
stability to air/water, easy isolation and avoidance of trimer
formation than normal arylboronic acids, have been exten-
sively used in the Suzuki–Miyaura coupling.8 Therefore, the
reactions between a variety of sulfamates 3 and potassium phenyl-
trifluoroborate were also tested under identical conditions.
To our delight, all reactions proceeded smoothly to give the
desired coupling products 5 in moderate to high yields. It
seems that electron-neutral and -rich substituents on the
phenyl ring of sulfamates gave products 5aq and 5ar in low
yields, respectively (Table 4, entries 2 and 3). Heteroaryl sulfa-
mate 3i worked well to give product 5at in 84% yield (Table 4,
entry 7). It should also be noted that similar yields can be
achieved for the reactions of substrates 3a and 3f with phenyl-
boronic acid or potassium phenyltrifluoroborate, respectively
(Table 4, entry 1 vs. Table 2, entry 11; Table 4, entry 5 vs.
Table 3, entry 11).
Entrya 3 (R′)
4 (R)
Yieldb (%)
1
2
3b (H)
3b
4b (3-MeO)
4a (4-MeO)
4j (3,5-Me2)
4a
4a
4k (H)
4a
4b
5n, 81
5o, 92
5p, 81
5q, 85
5r, 81
5o, 83
5s, 95
5t, 93
5u, 85
5v, 90
5w, 81
5x, 85
5y, 83
5z, 87
5aa, 99
5ab, 60
5ac, 50
5ad, 80
3
4
3c (3-Me)
3c
5
6
3d (4-MeO)
3d
7
8
3e (3-F)
3e
9
3e
3e
3f (4-Ac)
3f
3f
3f
3g (4-CF3)
3h (3-CHO)
3h (3-CHO)
3f
4h (3-F)
4n (4-CF3)
4k
10
11
12
13
14
15
16c
17c
18
4a
4d (4-Me)
4b
4k
4k
4g (4-F)
19
3f
5ae, 87
20
21
22
3b
3i
4m
4a
4d
5af, 83
5ag, 98
5ah, 95
23
24
3i
4b
4a
5ai, 97
5aj, 82
Table 4 NHC–Pd(II)–Mp complex 2a catalyzed coupling of sulfamates 3 with
potassium phenyltrifluoroborate under optimal conditions
25
26
3k
4a
4d
5ak, 86
5al, 94
27
4a
5am, 92
Entrya
3 (R′)
Yieldb (%)
1
2
3
4
5
6
3a (4-F)
3a (H)
3a (3-Me)
3a (3-F)
3a (4-Ac)
3a (4-CF3)
5k, 84
28
29
30
3l
3m
4d
4a
4d
5an, 94
5ao, 87
5ap, 94
5aq, 66
5ar, 72
5as, 82
5w, 80
5aa, 81
7
5at, 84
a All reactions were carried out using 3 (0.7 mmol), 4 (1.2 equiv.), 2a
(2.0 mol%), and Cs2CO3 (3.0 equiv.) in the morpholine (1.0 mL) and
H2O (0.1 mL) at 110 °C for 12 h. b Isolated yields. c The temperature
was 130 °C.
a All reactions were carried out using
3
(0.7 mmol), PhBF3K
(1.2 equiv.), 2a (2.0 mol%), and Cs2CO3 (3.0 equiv.) in morpholine
(1.0 mL) and H2O (0.1 mL) at 110 °C for 12 h. b Isolated yields.
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3.07–3.02 (m, 6H), 2.50–2.41 (m, 3H), 1.45 (d, J = 6.5 Hz, 12H),
1.10 (d, J = 6.5 Hz, 12H). 13C NMR (75 MHz, CDCl3) δ 156.9,
Conclusions
In conclusion, we have reported the first example so far of the 146.5, 135.0, 130.1, 124.8, 123.8, 67.6, 46.9, 28.6, 26.2, 23.1.
phosphine-free, NHC–Pd(II)–Mp complexes catalyzed Suzuki–
Compound 2b: a yellow solid. Mp: 274 °C (decomposed). 1H
Miyaura coupling of aryl sulfamates with arylboronic acids or NMR (300 MHz, CDCl3, TMS) δ 7.34 (dd, J = 8.4, 6.6 Hz, 2H),
potassium phenyltrifluoroborate in this paper. The Suzuki– 7.25–7.22 (m, 4H), 7.08 (s, 2H), 3.60 (dd, J = 12.0, 3.3 Hz, 2H),
Miyaura coupling can tolerate a variety of substrates. Under 3.24 (td, J = 12.0, 2.1 Hz, 2H), 3.06–2.93 (m, 2H), 2.48–2.44 (m,
optimal conditions, most reactions proceeded smoothly to give 2H), 2.35 (s, 12H). 13C NMR (125 MHz, CDCl3) δ 154.9, 137.4,
the desired coupling products in moderate to high yields. The 136.6, 129.4, 128.3, 123.8, 67.6, 46.9, 19.0. IR (ν): 1474, 1437,
NHC–Pd(II)–Mp complexes 2, which are air-, thermal- and 1255, 1092, 1049, 892, 874, 769, 748, 708 cm−1. MS (ESI) 540
moisture-stable, can be easily prepared from commercially [M + H]+; HRMS (ESI) calcd for C23H30Cl2N3OPd [M + H]+:
available imidazolium salts, PdCl2 and morpholine in a one- 540.0798, found: 540.0826. Anal. calcd for C25H34Cl2N3OPd:
pot procedure in high yields, thus making the procedure more requires C, 52.69%; H, 6.01%, N, 7.37%; found: C, 53.22%; H,
practical in organic synthesis.
5.90%, N, 7.08%.
Compound 2c: a yellow solid. Mp: 278 °C (decomposed). 1H
NMR (300 MHz, CDCl3, TMS) δ 7.04 (s, 4H), 7.02 (s, 2H), 3.62
(dd, J = 12.1, 3.0 Hz, 2H), 3.25 (td, J = 12.0, 2.1 Hz, 2H),
3.08–3.00 (m, 2H), 2.52–2.47 (m, 2H), 2.37 (s, 6H), 2.30 (s,
12H). 13C NMR (125 MHz, CDCl3) δ 154.7, 139.0, 136.2, 135.0,
129.0, 123.9, 67.6, 46.9, 21.1, 18.9. IR (ν): 1480, 1437, 1255,
1109, 1092, 1049, 892, 880, 744, 733, 695 cm−1. MS (ESI) 568
[M + H]+; HRMS (ESI) calcd for C25H34Cl2N3OPd [M + H]+:
568.1112, found: 568.1133. Anal. calcd for C23H30Cl2N3OPd:
requires C, 50.98%; H, 5.58%, N, 7.76%; found: C, 50.89%; H,
5.42%, N, 7.58%.
Experimental
General remarks
Melting points are uncorrected. NMR spectra were recorded at
1
300/500 (for H NMR) or 75/125 MHz (for 13C NMR), respect-
1
ively. H NMR and 13C NMR spectra recorded in CDCl3 solu-
tions were referenced to TMS (0.00 ppm) and the residual
solvent peak (77.0 ppm), respectively. J-values are given in Hz.
Organic solvents used were dried by standard methods. The
mass analyzer type for the high resolution mass spectra
(HRMS) is quadrupole (for ESI†). Other commercially obtained
reagents were used without further purification. Flash column
chromatography was performed on silica gel (300–400 mesh)
using CH2Cl2 (for complexes 2) and petroleum ether (for com-
pounds 5) as the eluents, respectively.
Compound 5a:3 a white solid. 1H NMR (300 MHz, CDCl3,
TMS) δ 7.35–7.30 (m, 4H), 7.07 (t, J = 5.1 Hz, 2H), 6.94 (d, J =
5.1 Hz, 2H), 3.81 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 162.0
(d, JC–F = 244.0 Hz), 159.1, 136.9 (d, JC–F = 3.3 Hz), 132.7, 128.1
(d, JC–F = 7.9 Hz), 128.0, 115.5 (d, JC–F = 21.3 Hz), 114.2, 55.2.
Compound 5b:3 a light yellow oil. 1H NMR (500 MHz,
CDCl3, TMS) δ 7.53 (dd, J = 8.5, 5.0 Hz, 2H), 7.34 (t, J = 7.0 Hz,
1H), 7.13–7.06 (m, 4H), 6.89 (dd, J = 8.0, 2.0 Hz, 1H), 3.85 (s,
3H). 13C NMR (125 MHz, CDCl3) δ 162.5 (d, JC–F = 244.9 Hz),
General procedure for the synthesis of NHC–Pd(II)–Mp
complexes 2
Under a N2 atmosphere, a mixture of imidazolium salts 1
(0.6 mmol), PdCl2 (0.57 mmol), K2CO3 (0.6 mmol) and mor-
pholine (2.4 mmol) was stirred in anhydrous THF (2.0 mL)
under reflux for 20 h. Then the solvent was removed under
reduced pressure, and the residue was purified by flash chrom-
atography on silica gel (CH2Cl2) to give the pure NHC–Pd(II)–
Mp complexes 2 as yellow solids.
159.9, 141.7, 137.1 (d, JC–F = 3.3 Hz), 129.8, 128.7 (d, JC–F
8.0 Hz), 119.5, 115.6 (d, JC–F = 21.4 Hz), 112.8, 112.5, 55.3.
=
Compound 5c:3 a pale yellow solid. 1H NMR (500 MHz,
CDCl3, TMS) δ 7.40–7.35 (m, 2H), 7.22–7.16 (m, 2H), 7.00–6.84
(m, 4H), 3.67 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 161.9 (d,
JC–F = 244.3 Hz), 156.3, 134.4 (d, JC–F = 3.0 Hz), 131.1 (d, JC–F
=
7.8 Hz), 130.7, 129.6, 128.7, 120.8, 114.8 (d, JC–F = 21.1 Hz),
111.2, 55.4.
General procedure for the NHC–Pd(II)–Mp complex
2a-catalyzed Suzuki–Miyaura coupling of aryl sulfamates with
arylboronic acids
Compound 5d:3 a pale yellow solid. 1H NMR (300 MHz,
CDCl3, TMS) δ 7.52–7.44 (m, 2H), 7.40 (d, J = 8.1 Hz, 2H), 7.20
(d, J = 8.1 Hz, 2H), 7.11–7.03 (m, 2H), 2.36 (s, 3H). 13C NMR
Under a N2 atmosphere, sulfamates 3 (0.7 mmol), arylboronic (125 MHz, CDCl3) δ 162.2 (d, JC–F = 244.4 Hz), 137.3, 137.2 (d,
acids or potassium phenyltrifluoroborate 4 (0.84 mmol), the JC–F = 2.9 Hz), 136.9, 129.5, 128.4 (d, JC–F = 7.8 Hz), 126.8, 115.5
NHC–Pd(II)–Mp complex 2a (2.0 mol%), Cs2CO3 (3.0 equiv.), (d, JC–F = 21.3 Hz), 21.0.
morpholine (1.0 mL) and H2O (0.1 mL) were successively
Compound 5e:3 a pale yellow oil. 1H NMR (300 MHz,
added into a Schlenk reaction tube. The mixture was stirred CDCl3, TMS) δ 7.51–7.46 (m, 2H), 7.31–7.28 (m, 3H), 7.13–7.03
vigorously at 110 °C for 12 h. Then the solvent was removed (m, 3H), 2.37 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 162.4 (d,
under reduced pressure and the residue was purified by flash JC–F = 244.6 Hz), 140.2, 138.4, 137.4 (d, JC–F = 3.0 Hz), 128.7,
column chromatography (SiO2) to give the pure products.
128.6 (d, JC–F = 8.0 Hz), 128.0, 115.5 (d, JC–F = 21.3 Hz), 21.5.
Compound 5f:3 a pale yellow oil. 1H NMR (500 MHz, CDCl3,
1
Compound 2a:3 a yellow solid. H NMR (500 MHz, CDCl3,
TMS) δ 7.50 (t, J = 8.0 Hz, 2H), 7.35 (d, J = 8.0 Hz, 4H), 7.09 (s, TMS) δ 7.26–7.18 (m, 6H), 7.06 (t, J = 8.5 Hz, 2H), 2.23 (s, 3H).
2H), 3.60 (dd, J = 12.0, 3.0 Hz, 2H), 3.26–3.21 (m, 2H), 13C NMR (125 MHz, CDCl3) δ 161.9 (d, JC–F = 244.1 Hz), 140.9,
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137.8 (d, JC–F = 3.4 Hz), 135.3, 130.7 (d, J = 7.9 Hz), 130.3, 3H). 13C NMR (125 MHz, CDCl3) δ 159.0, 140.7, 138.1, 133.7,
129.8, 127.4, 125.8, 114.9 (d, JC–F = 21.1 Hz), 20.4.
128.6, 128.0, 127.4, 127.3, 123.8, 114.0, 55.1, 21.5.
1
Compound 5g:9 a white solid. 1H NMR (300 MHz, CDCl3,
Compound 5r:11 a white solid. H NMR (500 MHz, CDCl3,
TMS) δ 7.48–7.41 (m, 4H), 7.12–7.04 (m, 4H). 13C NMR TMS) δ 7.47 (d, J = 9.0 Hz, 4H), 6.95 (d, J = 9.0 Hz, 4H), 3.84 (s,
(125 MHz, CDCl3) δ 162.4 (d, JC–F = 245.0 Hz), 136.4 (d, JC–F
3.3 Hz), 128.5 (d, JC–F = 8.0 Hz), 115.6 (d, JC–F = 21.3 Hz).
=
6H). 13C NMR (125 MHz, CDCl3) δ 158.7, 133.5, 127.7, 114.2,
55.3.
Compound 5h:3 a pale yellow oil. 1H NMR (500 MHz,
Compound 5s:12 a white solid. H NMR (300 MHz, CDCl3,
1
CDCl3, TMS) δ 7.49–7.46 (m, 2H), 7.35–7.31 (m, 1H), 7.27–7.25 TMS) δ 7.34 (d, J = 8.7 Hz, 2H), 7.23–7.08 (m, 4H), 6.81 (d, J =
(m, 1H), 7.20–7.17 (m, 1H), 7.10–7.06 (m, 2H), 7.01–6.97 (m, 8.7 Hz, 2H), 3.66 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 163.2 (d,
1H). 13C NMR (125 MHz, CDCl3) δ 163.2 (d, JC–F = 244.4 Hz), JC–F = 243.7 Hz), 159.5, 143.0 (d, JC–F = 7.7 Hz), 132.3 (d, JC–F
=
162.7 (d, JC–F = 245.9 Hz), 142.5 (d, JC–F = 7.6 Hz), 136.0 (dd, 2.3 Hz), 130.1 (d, JC–F = 8.3 Hz), 128.0, 122.2 (d, JC–F = 2.8 Hz),
JC–F = 2.8, 2.8 Hz), 130.3 (d, JC–F = 8.4 Hz), 128.7 (d, JC–F
8.0 Hz), 122.6 (d, JC–F = 2.6 Hz), 115.7 (d, JC–F = 21.4 Hz), 114.0
(d, JC–F = 21 Hz), 113.9 (d, JC–F = 21.9 Hz).
=
114.2, 113.4 (d, JC–F = 21.8 Hz), 113.3 (d, JC–F = 21.0 Hz), 55.2.
1
Compound 5t:13 a colorless oil. H NMR (300 MHz, CDCl3,
TMS) δ 7.39–7.28 (m, 4H), 7.26–7.00 (m, 3H), 6.91 (ddd, J = 8.1,
Compound 5j:3 a colorless oil. 1H NMR (500 MHz, CDCl3, 2.4, 0.9 Hz, 1H), 3.85 (s, 3H). 13C NMR (125 MHz, CDCl3) δ
TMS) δ 7.50 (dd, J = 8.5, 5.5 Hz, 2H), 7.14 (s, 2H), 7.08 (t, J = 8.5 Hz, 163.1 (d, JC–F = 244.0 Hz), 160.0, 143.4 (d, JC–F = 7.6 Hz), 141.4
2H), 6.98 (s, 1H), 2.36 (s, 6H). 13C NMR (125 MHz, CDCl3) (d, JC–F = 2.1 Hz), 130.1 (d, JC–F = 8.4 Hz), 129.9, 122.8 (d, JC–F
=
δ 162.3 (d, JC–F = 244.4 Hz), 140.3, 138.3, 137.5 (d, JC–F = 3.3 Hz), 2.6 Hz), 119.6, 114.1 (d, JC–F = 21.0 Hz), 114.0 (d, JC–F = 21.9
128.9, 128.6 (d, JC–F = 8.0 Hz), 124.9, 115.4 (d, JC–F = 21.3 Hz), Hz), 113.2, 112.9, 55.3.
1
21.3.
Compound 5u:14 a colorless oil. H NMR (500 MHz, CDCl3,
1
Compound 5k:10 a white solid. H NMR (300 MHz, CDCl3, TMS) δ 7.39–7.24 (m, 6H), 7.06–7.03 (m, 2H). 13C NMR
TMS) δ 7.53–7.49 (m, 4H), 7.40 (t, J = 7.2 Hz, 2H), 7.31 (t, J = (125 MHz, CDCl3) δ 163.2 (d, JC–F = 244.5 Hz), 142.2 (d, JC–F
=
7.2 Hz, 1H), 7.09 (t, J = 8.7 Hz, 2H). 13C NMR (75 MHz, CDCl3) 7.6 Hz), 130.4 (d, JC–F = 8.4 Hz), 122.7, 114.6 (d, JC–F = 21 Hz),
δ 162.4 (d, JC–F = 244.7 Hz), 140.2, 137.3 (d, JC–F = 3.4 Hz), 114.0 (d, JC–F = 22.1 Hz).
1
128.8, 128.6 (d, JC–F = 8.0 Hz), 127.2, 127.0, 115.6 (d, JC–F
=
Compound 5v:14 a colorless oil. H NMR (500 MHz, CDCl3,
21.2 Hz).
TMS) δ 7.67 (d, J = 8.5 Hz, 2H), 7.62 (d, J = 8.5 Hz, 2H),
Compound 5l:3 a white solid. 1H NMR (500 MHz, CDCl3, 7.42–7.38 (m, 1H), 7.34 (dt, J = 7.5, 1.5 Hz, 1H), 7.25 (dt, J =
TMS) δ 7.91–7.83 (m, 3H), 7.53–7.38 (m, 6H), 7.19–7.16 (m, 9.5, 2.0 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ 163.3 (d, JC–F
2H). 13C NMR (125 MHz, CDCl3) δ 162.2 (d, JC–F = 244.6 Hz), 244.9 Hz), 143.4, 142.0 (d, JC–F = 7.6 Hz), 130.5 (d, JC–F
=
=
139.1, 136.6 (d, JC–F = 3.3 Hz), 133.8, 131.6, 131.5 (d, JC–F
8.0 Hz), 128.3, 127.9, 127.8, 127.0, 126.1, 125.83, 125.80, 125.7, 124.2 (q, JC–F = 270.4 Hz), 122.9 (d, JC–F = 2.9 Hz), 115.0 (d, JC–F
125.3, 115.2 (d, JC–F = 21.1 Hz). = 21.1 Hz), 114.2 (d, JC–F = 22.1 Hz).
Compound 5m:3 a white solid. H NMR (500 MHz, CDCl3,
=
8.0 Hz), 130.0 (q, JC–F = 32.4 Hz), 127.4, 125.8 (q, JC–F = 3.6 Hz),
1
1
Compound 5w:10 a white solid. H NMR (300 MHz, CDCl3,
TMS) δ 7.91 (s, 1H), 7.83–7.79 (m, 3H), 7.61–7.56 (m, 3H), TMS) δ 8.02 (d, J = 8.7 Hz, 2H), 7.68–7.60 (m, 4H), 7.46–7.36
7.46–7.42 (m, 2H), 7.10 (t, J = 8.5 Hz, 2H). 13C NMR (125 MHz, (m, 3H), 2.62 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 197.7,
CDCl3) δ 162.5 (d, JC–F = 245.1 Hz), 137.5, 137.1 (d, JC–F
=
145.7, 139.8, 135.8, 128.90, 128.86, 128.2, 127.20, 127.15,
3.1 Hz), 133.6, 132.5, 128.9 (d, JC–F = 8.0 Hz), 128.5, 128.1, 26.6.
1
127.6, 126.3, 125.9, 125.6, 125.3, 115.6 (d, JC–F = 21.3 Hz).
Compound 5x:15 a white solid. H NMR (300 MHz, CDCl3,
1
Compound 5n:3 a colorless oil. H NMR (300 MHz, CDCl3, TMS) δ 8.00 (d, J = 8.7 Hz, 2H), 7.63 (d, J = 8.7 Hz, 2H), 7.57 (d,
TMS) δ 7.58–7.54 (m, 2H), 7.42–7.28 (m, 4H), 7.17–7.11 (m, J = 9.0 Hz, 2H), 6.99 (d, J = 9.0 Hz, 2H), 3.85 (s, 3H), 2.62 (s,
2H), 6.86 (ddd, J = 8.1, 2.4, 0.9 Hz, 1H), 3.80 (s, 3H). 13C NMR 3H). 13C NMR (125 MHz, CDCl3) δ 197.6, 159.8, 145.2, 135.2,
(125 MHz, CDCl3) δ 159.9, 142.7, 141.1, 129.7, 128.7, 127.4, 132.1, 128.9, 128.3, 126.5, 114.3, 55.3, 26.5.
1
127.1, 119.6, 112.8, 112.6, 55.2.
Compound 5y:15 a white solid. H NMR (300 MHz, CDCl3,
Compound 5o:3 a white solid. 1H NMR (500 MHz, CDCl3, TMS) δ 8.00 (d, J = 8.4 Hz, 2H), 7.65 (d, J = 8.4 Hz, 2H), 7.51 (d,
TMS) δ 7.45–7.41 (m, 4H), 7.30 (t, J = 7.5 Hz, 2H), 7.19 (t, J = J = 8.1 Hz, 2H), 7.26 (d, J = 8.1 Hz, 2H), 2.61 (s, 3H), 2.39 (s,
7.5 Hz, 1H), 6.86 (d, J = 8.5 Hz, 2H), 3.71 (s, 3H). 13C NMR 3H). 13C NMR (75 MHz, CDCl3) δ 197.7, 145.6, 138.2, 136.9,
(75 MHz, CDCl3) δ 159.1, 140.7, 133.7, 128.7, 128.1, 127.7, 135.5, 129.6, 128.8, 127.0, 126.9, 26.6, 21.1.
1
126.7, 114.1, 55.2.
Compound 5z:16 a colorless oil. H NMR (300 MHz, CDCl3,
Compound 5p:3 a colorless oil. H NMR (500 MHz, CDCl3, TMS) δ 7.99 (d, J = 8.1 Hz, 2H), 7.64 (d, J = 8.1 Hz, 2H), 7.35 (t,
TMS) δ 7.38–7.35 (m, 2H), 7.28 (t, J = 7.5 Hz, 1H), 7.18 (s, 2H), J = 7.8 Hz, 1H), 7.18 (d, J = 7.8 Hz, 1H), 7.13 (t, J = 2.1 Hz, 1H),
7.11 (d, J = 7.5 Hz, 1H), 6.96 (s, 1H), 2.38 (s, 3H), 2.35 (s, 6H). 6.92 (dd, J = 8.1, 2.1 Hz, 1H), 3.84 (s, 3H), 2.59 (s, 3H). 13C
13C NMR (125 MHz, CDCl3) δ 141.4, 141.3, 138.1, 128.8, 128.5, NMR (75 MHz, CDCl3) δ 197.5, 159.9, 145.3, 141.1, 135.7,
1
127.9, 127.8, 125.1, 124.3, 21.5, 21.4.
129.8, 128.7, 127.0, 119.5, 113.3, 112.9, 55.1, 26.4.
1
Compound 5q:3 a pale yellow solid. 1H NMR (300 MHz,
Compound 5aa:17 a white solid. H NMR (500 MHz, CDCl3,
CDCl3, TMS) δ 7.39 (d, J = 8.7 Hz, 2H), 7.24–7.14 (m, 3H), 6.99 TMS) δ 7.69 (s, 4H), 7.60–7.58 (m, 2H), 7.47 (t, J = 7.5 Hz, 2H),
(d, J = 7.2 Hz, 1H), 6.83 (d, J = 8.7 Hz, 2H), 3.67 (s, 3H), 2.27 (s, 7.40 (t, J = 7.5 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ 144.7,
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139.8, 129.4 (q, JC–F = 32.3 Hz), 129.0, 128.2, 127.4, 127.3, 125.7 7.44 (d, J = 8.5 Hz, 2H), 7.31 (d, J = 4.5 Hz, 1H), 7.05 (d, J =
(q, JC–F = 3.8 Hz), 124.3 (q, JC–F = 270.3 Hz).
8.5 Hz, 2H), 3.89 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 159.8,
Compound 5ab:18 a colorless oil. 1H NMR (500 MHz, 149.6, 148.4, 148.3, 130.7, 130.0, 129.5, 129.3, 126.8, 126.5,
CDCl3, TMS) δ 10.07 (s, 1H), 8.08 (s, 1H), 7.84 (dd, J = 7.5, 1.5 Hz, 125.8, 121.2, 114.0, 55.3.
2H), 7.62–7.57 (m, 3H), 7.46 (t, J = 7.5 Hz, 2H), 7.38 (t, J =
7.5 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ 192.2, 142.1, 139.6, TMS) δ 8.81 (d, J = 4.5 Hz, 1H), 8.08 (d, J = 8.5 Hz, 1H),
136.9, 133.0, 129.4, 128.9, 128.5, 128.1, 127.9, 127.1. 7.84 (dd, J = 8.5, 1.0 Hz, 1H), 7.60 (t, J = 8.5 Hz, 1H), 7.38–7.35
Compound 5al:24 a colorless oil. 1H NMR (500 MHz, CDCl3,
Compound 5ac:19 a colorless oil. 1H NMR (500 MHz, CDCl3, (m, 1H), 7.28 (d, J = 8.5 Hz, 2H), 7.22–7.00 (m, 3H), 2.34 (s,
TMS) δ 10.07 (s, 1H), 8.04 (s, 1H), 7.84 (d, J = 7.5 Hz, 1H), 7.79 3H). 13C NMR (125 MHz, CDCl3) δ 149.7, 148.6, 148.4, 138.3,
(d, J = 7.5 Hz, 1H), 7.60–7.56 (m, 3H), 7.15 (t, J = 8.5 Hz, 2H). 134.9, 129.5, 129.3, 129.24, 129.18, 126.7, 126.5, 125.8, 121.2,
13C NMR (125 MHz, CDCl3) δ 192.1, 162.8 (d, JC–F = 246.1 Hz), 21.2.
141.1, 136.9, 135.8 (d, JC–F = 3.25 Hz), 132.8, 129.5, 128.71 (d,
Compound 5am:22 a white solid. 1H NMR (500 MHz, CDCl3,
TMS) δ 8.95 (d, J = 4.0 Hz, 1H), 8.15 (dd, J = 8.5, 1.5 Hz, 1H),
JC–F = 8.25 Hz), 128.68, 127.7, 115.9 (d, JC–F = 21.5 Hz).
1
Compound 5ad:20 a white solid. H NMR (300 MHz, CDCl3, 7.75 (dd, J = 8.5, 1.5 Hz, 1H), 7.69 (d, J = 7.0 Hz, 1H), 7.65 (d,
TMS) δ 8.09 (d, J = 8.4 Hz, 2H), 7.91 (t, J = 7.8 Hz, 2H), 7.84 (d, J = 8.5 Hz, 2H), 7.55 (t, J = 7.5 Hz, 1H), 7.36 (dd, J = 8.5, 4.0 Hz,
J = 8.4 Hz, 1H), 7.60 (d, J = 8.4 Hz, 2H), 7.57–7.41 (m, 4H), 2.68 1H), 7.04 (d, J = 8.5 Hz, 2H), 3.85 (s, 3H). 13C NMR (125 MHz,
(s, 3H). 13C NMR (125 MHz, CDCl3) δ 197.8, 145.7, 139.0, CDCl3) δ 159.0, 150.0, 145.9, 140.3, 136.2, 131.7, 131.6, 129.9,
136.0, 133.8, 131.2, 130.3, 128.4, 128.3, 126.9, 126.3, 125.9, 128.7, 127.0, 126.2, 120.8, 113.5, 55.2.
125.5, 125.3, 26.6.
Compound 5an:25 a colorless oil. 1H NMR (500 MHz,
1
Compound 5ae:21 a white solid. H NMR (300 MHz, CDCl3, CDCl3, TMS) δ 8.79 (dd, J = 4.0, 1.5 Hz, 1H), 7.95 (dd, J = 8.0,
TMS) δ 8.02 (d, J = 8.4 Hz, 3H), 7.90–7.68 (m, 6H), 7.50–7.22 1.5 Hz, 1H), 7.59–7.54 (m, 2H), 7.46 (d, J = 8.0 Hz, 2H), 7.38 (t,
(m, 2H), 2.60 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 197.8, 145.7, J = 8.0 Hz, 1H), 7.18–7.15 (m, 3H), 2.27 (s, 3H). 13C NMR
137.1, 135.8, 133.5, 133.0, 129.0, 128.7, 128.3, 127.7, 127.5, (125 MHz, CDCl3) δ 149.9, 145.9, 140.7, 136.8, 136.4, 136.0,
126.6, 126.5, 126.4, 125.2, 26.7.
Compound 5af:3 a white solid. H NMR (500 MHz, CDCl3,
130.3, 129.9, 128.6, 128.5, 127.1, 126.1, 120.7, 21.1.
1
1
Compound 5ao:26 a white solid. H NMR (500 MHz, CDCl3,
TMS) δ 8.00 (s, 1H), 7.86–7.80 (m, 3H). 7.71–7.67 (m, 3H), TMS) δ 8.73 (dd, J = 4.5, 1.5 Hz, 1H), 8.01 (d, J = 8.5 Hz, 1H),
7.47–7.42 (m, 4H), 7.33 (t, J = 7.5 Hz, 1H). 13C NMR (125 MHz, 7.95 (d, J = 8.5 Hz, 1H), 7.78 (dd, J = 8.5, 2.0 Hz, 1H), 7.73 (d,
CDCl3) δ 141.0, 138.5, 133.6, 132.6, 128.8, 128.4, 128.2, 127.6, J = 2.0 Hz, 1H), 7.47 (d, J = 8.5 Hz, 2H), 7.20 (dd, J = 8.5, 4.5 Hz,
127.4, 127.3, 126.2, 125.9, 125.7, 125.5.
1H), 6.85 (d, J = 8.5 Hz, 2H), 3.68 (s, 3H). 13C NMR (125 MHz,
Compound 5ag:3 a pale yellow solid. 1H NMR (500 MHz, CDCl3) δ 159.3, 149.7, 147.0, 138.6, 136.0, 132.4, 129.5, 128.8,
CDCl3, TMS) δ 8.70 (d, J = 1.5 Hz, 1H), 8.42 (d, J = 4.5 Hz, 1H), 128.3, 128.2, 124.4, 121.2, 114.2, 55.1.
1
7.69 (d, J = 8.0 Hz, 1H), 7.38 (d, J = 8.0 Hz, 2H), 7.19 (dd, J =
Compound 5ap:26 a white solid. H NMR (500 MHz, CDCl3,
8.0, 5.0 Hz, 1H), 6.88 (d, J = 9.0 Hz, 2H), 3.71 (s, 3H). 13C NMR TMS) δ 8.73 (dd, J = 4.0, 1.5 Hz, 1H), 8.03 (d, J = 9.0 Hz, 1H),
(75 MHz, CDCl3) δ 159.5, 147.6, 147.5, 136.0, 133.7, 129.9, 7.96 (d, J = 8.5 Hz, 1H), 7.80 (dd, J = 9.0, 2.0 Hz, 1H), 7.77 (s,
128.0, 123.3, 114.3, 55.1.
1H), 7.43 (d, J = 8.0 Hz, 2H), 7.20 (dd, J = 8.5, 3.6 Hz, 1H), 7.12
Compound 5ah:12 a pale yellow oil. 1H NMR (300 MHz, (d, J = 8.0 Hz, 2H), 2.25 (s, 3H). 13C NMR (125 MHz, CDCl3) δ
CDCl3, TMS) δ 8.82 (d, J = 2.4 Hz, 1H), 8.54 (dd, J = 4.8, 1.5 Hz, 149.9, 147.2, 139.0, 137.4, 137.1, 136.1, 129.5, 129.0, 128.3,
1H), 7.80 (dt, J = 8.1, 1.5 Hz, 1H), 7.44 (d, J = 8.1 Hz, 2H), 127.0, 124.8, 121.2, 21.0.
1
7.30–7.23 (m, 3H), 2.37 (s, 3H). 13C NMR (125 MHz, CDCl3) δ
Compound 5aq:15 a white solid. H NMR (500 MHz, CDCl3,
147.9, 137.7, 136.3, 134.6, 133.8, 129.6, 126.7, 123.2, 20.9.
TMS) δ 7.58–7.56 (m, 4H), 7.41 (t, J = 7.5 Hz, 4H), 7.31 (t, J =
Compound 5ai:12 a pale yellow oil. 1H NMR (300 MHz, 7.5 Hz, 2H). 13C NMR (125 MHz, CDCl3) δ 141.2, 128.7, 127.2,
CDCl3, TMS) δ 8.84 (d, J = 2.1 Hz, 1H), 8.57 (dd, J = 4.8, 1.5 Hz, 127.1.
1H), 7.83 (dt, J = 7.8, 1.8 Hz, 1H), 7.39–7.30 (m, 2H), 7.15–7.08
1
Compound 5ar:3 a colorless oil. H NMR (300 MHz, CDCl3,
(m, 2H), 7.09 (t, J = 1.8 Hz, 1H), 6.93 (ddd, J = 8.1, 2.4, 0.6 Hz, TMS) δ 7.59–7.56 (m, 2H), 7.43–7.37 (m, 4H), 7.31 (t, J = 7.2 Hz,
1H), 3.83 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 160.0, 148.3, 2H), 7.14 (d, J = 7.2 Hz, 1H), 2.40 (s, 3H). 13C NMR (125 MHz,
148.1, 139.1, 136.3, 134.2, 129.9, 123.3, 119.4, 113.2, 112.8, CDCl3) δ 141.4, 141.2, 138.3, 128.7, 128.6, 127.97, 127.95,
55.1.
Compound 5aj:22 a pale yellow oil. 1H NMR (300 MHz,
127.15, 127.13, 124.3, 21.5.
Compound 5as:13 a colorless oil. 1H NMR (300 MHz, CDCl3,
CDCl3, TMS) δ 8.64–8.61 (m, 1H), 7.94 (dt, J = 3.0, 9.6 Hz, 2H), TMS) δ 7.56–7.52 (m, 2H), 7.44–7.24 (m, 6H), 7.04–6.98 (m,
7.67–7.59 (m, 2H), 7.11 (ddd, J = 2.1, 4.8, 7.2 Hz, 1H), 6.97 (dt, 1H). 13C NMR (125 MHz, CDCl3) δ 163.2 (d, JC–F = 244.0 Hz),
J = 2.7, 9.6 Hz, 2H), 3.80 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 143.5 (d, JC–F = 7.6 Hz), 139.9 (d, JC–F = 2.1 Hz), 130.2 (d, JC–F
=
160.3, 156.9, 149.3, 136.4, 131.8, 128.0, 121.2, 119.6, 113.9, 8.4 Hz), 128.9, 127.8, 127.1, 122.7 (d, JC–F = 2.8 Hz), 114.0 (d,
55.1.
Compound 5ak:23 a white solid. H NMR (500 MHz, CDCl3,
JC–F = 20.6 Hz), 113.9.
1
Compound 5at:15 a pale yellow oil. 1H NMR (300 MHz,
TMS) δ 8.91 (d, J = 4.5 Hz, 1H), 8.19 (d, J = 8.5 Hz, 1H), 7.97 (d, CDCl3, TMS) δ 8.84 (d, J = 2.1 Hz, 1H), 8.58 (dd, J = 4.8, 1.5 Hz,
J = 8.5 Hz, 1H), 7.72 (t, J = 7.5 Hz, 1H), 7.50 (t, J = 7.5 Hz, 1H), 1H), 7.84 (dt, J = 8.1, 1.8 Hz, 1H), 7.57–7.31 (m, 6H). 13C NMR
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(125 MHz, CDCl3) δ 148.3, 148.2, 137.7, 136.5, 134.2, 128.9,
127.9, 127.0, 123.4.
F. Beaumard, Org. Lett., 2010, 12, 4022; (m) K. W. Quasdorf,
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Acknowledgements
Financial support from the Natural Science Foundation of
Zhejiang Province (no. LY12B02012) and the Open Research
Fund of Top Key Discipline of Chemistry in Zhejiang Provincial
Colleges and Key Laboratory of the Ministry of Education for
Advanced Catalysis Materials (Zhejiang Normal University)
(no. ZJHX201305) is greatly appreciated.
5 For some other selected papers using aryl sulfamates as
the substrates, please see: (a) T. Agrawal and S. P. Cook,
Org. Lett., 2013, 15, 96; (b) A. L. Silberstein, S. D. Ramgren
and N. K. Garg, Org. Lett., 2012, 14, 3796; (c) H. Tadaoka
and T. Yamakawa, Tetrahedron Lett., 2012, 53, 5531;
(d) L. Hie, S. D. Ramgren, T. Mesganaw and N. K. Garg,
Org. Lett., 2012, 14, 4182; (e) W.-F. Song and L. Ackermann,
Angew. Chem., Int. Ed., 2012, 51, 8251; (f) L. Ackermann,
R. Sandmann and W.-F. Song, Org. Lett., 2011, 13, 1784;
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6 L. Zhu, T.-T. Gao and L.-X. Shao, Tetrahedron, 2011, 67,
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4087; (b) T. Thiemann, K. Umeno, D. Ohira, E. Inohae,
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8 For reviews of organotrifluoroborate alkali metal salts,
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