Tryptophan/copper-catalyzed aromatization reaction of chiral cyclohexanones to phenols

Article abstract of DOI:10.1039/c7ob01114h

By merging organocatalysis with copper catalysis, a highly efficient stereospecific approach for the synthesis of chiral phenols from cyclohexanones has been developed for the first time. The aromatization reaction proceeds through the in situ formation of enone intermediates and further subsequent bromination/dehydrobromination reactions. And a series of functionalized phenol derivatives are obtained in good yields (up to 89%) and good to excellent enantioselectivities (up to 99% ee).

Full text of DOI:10.1039/c7ob01114h

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Tryptophan/Copper-Catalyzed Aromatization Reaction of Chiral
Cyclohexanones to Phenols
Received 00th January 20xx,
Accepted 00th January 20xx
Xue-Li Liu, Xiao-Long Zhang, Ai-Bao Xia,* Yan-Jun Guo, Chen-Hong Meng, and Dan-Qian Xu*
DOI: 10.1039/x0xx00000x
www.rsc.org/
By merging organocatalysis with copper catalysis, a highly efficient (Scheme 1).9d However, few examples of Cu-catalyzed
stereospecific approach for the synthesis of chiral phenols from aromatization are involved in cyclohexanones, which are
cyclohexanones has been developed for the first time. The
aromatization reaction proceeds through in situ formation of
enone
intermediates
and
subsequent
further
bromination/dehydrobromination reactions. And a series of
functionalized phenol derivatives are obtained in good yields (up
to 89%) and good to excellent enantioselectivities (up to 99% ee).
Chiral 2-(1-phenylethyl)phenols is one of the representative
structural
pharmaceuticals, and biologically active compounds (Figure
motifs
in
numerous
natural
products,
1
).1 From a synthetic viewpoint, the development of methods
2
to construct phenols is a topic of growing interest. Among
such methods, transition-metal-catalyzed aromatization of
Figure 1. Selected examples of pharmacologically active chiral
phenol derivatives.
cyclic
cyclohexenones, has recently emerged as an attractive
compounds,
such
as
cyclohexanones
and
3
approach for preparing various phenol derivatives. Precious
metals, such as iridium,3d,4 palladium, ruthenium, gold, and
rhodium4b,8 could convert cyclohexanones or cyclohexenones
into phenol derivatives. On the other hand, non-precious
metal, especially for copper salts, could serve as effective
5
6
7
9
catalysts to transform cyclohexenones into phenols. In 2013,
Kikushima and Nishina developed a catalytic oxidative
aromatization reaction of 2-cyclohexenones to afford phenol
2
derivatives in the presence of a catalytic amount of CuBr and
aqueous HBr under molecular oxygen (Scheme 1).9c Later,
Reddy, Liu and co-workers described a catalytic method to
convert substituted cyclohexenones into corresponding
phenols
dehydrobromination reaction using copper acetate as the
catalyst in the presence of LiBr and CF COOH under oxygen
and
bromophenols
via
bromination/
3
Catalytic Hydrogenation Research Centre, State Key Laboratory Breeding Base of
Green Chemistry-Synthesis Technology, Zhejiang University of Technology,
Hangzhou, 310014, China; E-mail: xiaaibao@zjut.edu.cn, chrc@zjut.edu.cn.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
Scheme 1. Other methods and our approach to phenol derivatives.
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in elimination step of bromination/dehydroVibewroAmrticilne aOtniloinne
Table 1. Optimization of the aromatization of 3a’ under aromatization reaction,9d we envisaged t Dh Oa tI : 1s 0y .n1 0t h3 9e / sCi s7 Oo Bf0 c1 1h 1i 4r Ha l
various reaction conditions.[a]
phenol derivatives from cyclohexanones might be well realized
by in situ formation of enone intermediates, via enamine-
catalyzed α-bromination and copper-catalyzed dehydro-
bromination, and subsequent further bromination/dehydro-
bromination (Scheme 1). Thus, we herein report
a
tryptophan/copper-catalyzed aromatization reaction of chiral
cyclohexanones, which can be synthesized by the well-
developed Michael reactions of cyclohexanones with
nitroolefins, to synthesize a series of chiral γ-nitrophenols with
excellent enantioselectivities.
In order to explore the feasibility, the racemic γ-
nitrocycloalkanone of 4-methyl-2-(2-nitro-1-phenylethyl)-
cyclohexanone 3a’ was selected as a model substrate (Table 1).
The first study began with the reaction of 3a’ and 2.0 equiv.
dimethyl 2,2-dibromomalonate under the catalysis of 50 mol %
Yield(%)[b]
Entry
Catalyst
5a
/
Lewis acid
/
1
2
3
4
5
6
7
8
9
none
none
16
CuBr2
CuBr2
CuBr2
CuBr2
CuBr2
CuBr2
CuBr2
CuBr2
CuBr2
3
glycine 5a in CH CN at 100 °C (oil bath) for 2 h with 50 mol %
5a
5b
5c
PhCOOH as the additive acid (entry 1). However, none of the
desired product was observed, the majority of the starting
material 3a’ remained unreacted. The same negative result
42
57
5d
5e
5f
76
was achieved under the catalysis of 15 mol % CuBr
To our delight, as expected, the desired aromatization product
2
(entry 2).
10
29
4
5
a’ was isolated in 16% yield under the cooperative catalysis of
and CuBr (entry 3). Then, a number of experiments were
5k 5d was the most
5g
5h
5i
56
a
2
10
11
12
13
30
further tested. Among organocatalysts 5a
- ,
CuBr2
35
suitable catalyst for the aromatization reaction to give product
racemic 4a’ in 76% yield (entries 3-13), 50 mol% loading of 5d
proved to be a suitable amount among the screened record
(entries 6, 14-15). Other tested Lewis acid catalysts like CuSO4,
5j
CuBr2
19
5k
5d
5d
5d
5d
5d
5d
5d
5d
5d
5d
CuBr2
nd
56
1
4[c]
CuBr2
1
5[d]
CuBr2
60
Cu(OAc)
2
, CuCl
(entries 16-19), and the best result was obtained with CuBr
2
·2H
2
O and Zn(OAc)
2
gave up to 42% yields
in
1
6
7
8
9
CuSO4
Cu(OAc)2
20
2
1
42
15 mol% loading (entries 6, 20-22). Further investigations on
the additive acids, brominating agents, reaction temperature
and various solvents did not afford better results (see Table S1
in the Supporting Information for details). When the reaction
was carried out in nitrogen atmosphere, almost the same
reaction performance was observed (entries 6, 23). This
observation might indicate oxygen had limited influence on
the reaction (entry 23). Therefore, the optimal reaction
conditions were determined to be the following: tryptophan
.
1
1
CuCl 2H O
2
17
2
Zn(OAc)2
CuBr2
10<
53
0[e]
2
1[f]
2
CuBr2
60
2[g]
2
CuBr2
55
2
3[h]
CuBr2
75
[a]Unless otherwise stated, the reaction was carried out in 10 mL sealed
tube using solvent (1.0 mL), dimethyl 2,2-dibromomalonate (0.2 mmol) and
(
50 mol %), PhCOOH (50 mol %), 2.0 equiv. dimethyl 2,2-
dibromomalonate and CuBr (15 mol %) in CH CN at 100 °C for
h.
3
a’ (0.1 mmol) with 50 mol % 5, 50 mol % PhCOOH and 15 mol % Lewis acid
at 100°C for 2h. [b]Isolated yields after column chromatography. [c]20 mol%
d was used. [d]100 mol% 5d was used. [e]10 mol% CuBr was used. [f]30
mol% CuBr
was used. [g]50 mol% CuBr was used. [h]Under Nitrogen.
2
3
2
5
2
Attempt was further made to determine and evaluate
whether or not the aromatization methodology could apply to
chiral γ-nitroketones. The prolinethiol ether (S)-2-((pyrrolidin-
2
2
commercially available, stable and widely used as raw
materials to prepare many important bulk chemicals.9d In
addition, the chiral example still remains an issue for this kind
of transformation.
2
-ylmethyl)thio)pyridine
for asymmetric Michael additions of ketones to nitroolefins to
synthesize γ-nitroketones , and the ee values of γ-
6 were chosen as the organocatalyst
3
nitroketones were listed in Table 2.12 Under the optimized
aromatization conditions, the complete conversion of chiral γ-
nitroketone 3a resulted in the formation of the corresponding
target product 4a in 76% yield and 95% ee (Table 2, entry 1).
Then the scope of this reaction was further examined. As
In recent years, cooperative catalysis by merging
organocatalysis and transition-metal catalysis has enabled a
series of new enantioselective methodologies.10 Among these,
the use of enamine/transition-metal catalysis has been widely
investigated for asymmetric reactions, but a few examples
involve in metal copper.11 Owing to the key role of copper ions
shown in Table 2, in general, the aromatization reaction proceeded
smoothly. 60% to 89% yields with 90% to 99% enantioselectivities
2
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group with methoxyl, methyl, halogen functionaVliegwroArutipcles,Onalnined
DOI: 10.1039/C7OB01114H
even naphthyl group, were very suitable substrates to give the
Table 2. Substrate scope for the sequential catalysis.[a]
products with the isolated yields of 60% to 81% and ee values
of 90% to 99% (Entries 1-14). Moreover, the 4-
ethylcyclohexanones 3o and 3p also performed well and
produced 4o and 4p in 75% and 68% yield with corresponding
93% and 96% ee respectively (Entries 15-16). In addition, the
3-methylcyclohexanone 3q was tolerated under this procedure
to give the product 4q in 89% yield and 93% ee (Entry 17).
Yield
[
Ee
Ee
[%][d]
95
94
94
90
91
96
95
94
92
92
99
95
96
96
93
96
93
Entry
R1
R2
4
%][b] [%][c]
The absolute configuration (AC) of the aromatization
product 4b was determined to be S by comparing the
experimental CD spectrum with the results of time-dependent
1
2
3
4
5
6
7
8
9
4-Me
4-Me
4-Me
4-Me
4-Me
4-Me
4-Me
4-Me
H
Ph
4a
4b
4c
4d
4e
4f
76
73
65
70
72
66
60
63
81
72
65
62
65
63
75
68
89
96
99
93
98
92
99
99
97
93
97
96
99
96
97
98
95
93
4-MeO-Ph
3,4-MeO-Ph
4-Me-Ph
4-F-Ph
density functional theory (TDDFT) calculations of electronic
circular dichroism (ECD) spectra.13,14 As shown in Figure 2 in
the selected data in the 200-330 nm UV region, the experime-
2-Br-Ph
4-Br-Ph
2-Naphthyl
Ph
ntal CD spectrum is consistent with the calculated data of
configuration.
S
4g
4h
4i
10
11
12
13
14
15
16
17
H
3-MeO-Ph
3-Cl-Ph
4j
H
4k
4l
H
4-Cl-Ph
H
3-Br-Ph
4m
4n
4o
4p
4q
H
3
4-CF -Ph
4-Et
4-Et
3-Me
Ph
4-Br-Ph
Ph
[a]Unless otherwise stated, the reaction was carried out in 10 mL sealed
tube using CH CN (1.0 mL), dimethyl 2,2-dibromo-malonate (0.2 mmol) and
(0.1 mmol) with 50 mol % 5d, 50 mol % PhCOOH and 15 mol % CuBr at
00°C for 2h. [b]The isolated yields of 4 only for the aromatization step after
3
3
2
1
column chromatography. [c]The ees of 3 determined by chiral HPLC using
Chiralpak AS-H, AD-H, IC or OD-H columns. [d]The ees of compounds 4
determined by chiral HPLC using Chiralpak AD-H, IC or OD-H columns.
Scheme 2. Possible reaction pathway for the aromatization
reaction.
Based on the experimental results, and the previous
works on enamine catalyzed α-bromination of ketones and Cu-
catalyzed dehydrobromination aromatization of cyclic ketones,
a plausible reaction mechanism for the aromatization reaction
is illustrated in Scheme 2. In the first step, the catalyst
tryptophan 5d forms a enamine intermediate
nitrocycloalkanone , and this activation process is followed
quickly by the electrophilic attack of bromine from dimethyl
,2-dibromomalonate to form 2-monobrominated
Further quick dehydrobromination of
in the presence of CuBr leads to intermediate
A with the γ-
3
2
intermediate
intermediate
B.
B
2
C
. Hydrolysis by water affords the catalyst 5d and intermediate
which undergoes second bromination/dehydrobromination
D
followed by tautomerization to yield the desired phenol
product . The existence of the intermediate in the reaction
4
C
mixture was further confirmed using the ESI-MS.13 Further
mechanistic details are under investigation.
Figure 2. Experimental and calculated ECD spectra of the
aromatization product 4b
.
were obtained under the standard reaction conditions. 4-
Methylcyclohexanones and cyclohexanones, bearing phenyl
Conclusions
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(a) R. Ahuja, B. Punji, M. Findlater, Nat. Chem. 2011, , 167;
In conclusion, by merging organocatalysis with copper
catalysis, we have developed simple and efficient
methodology for the synthesis of chiral phenols for the first
time through tryptophan/CuBr catalyzed bromination/de-
4
5
3
View Article Online
(
2
b) S. Kusumoto, M. Akiyama, K. Noza
013, 135, 18726; (c) A. Kumar, A. S. Goldman, Topic.
Organometa. Chem. 2016, 54, 307.
ki, J. Am. Chem. Soc.
DOI: 10.1039/C7OB01114H
a
2
(a) Y. Shvo, A. H. I. Arisha, J. Org. Chem. 1998, 63, 5640; (b) Y.
Izawa, D. Pun, S. S. Stahl, Science 2011, 333, 209; (c) D. Pun, T.
Diao, S. S. Stahl, J. Am. Chem. Soc. 2013, 135, 8213; (d) Y.
Izawa, C. Zheng, S. S. Stahl, Angew. Chem. 2013, 125, 3760;
Angew. Chem. Int. Ed. 2013, 52, 3672; (e) A. V. Iosub, S. S.
Stahl, J. Am. Chem. Soc. 2013, 137, 3454; (f) J. W. Zhang, Q. Q.
Jiang, D. J. Yang, X. M. Zhao, Y. L. Dong, R. H. Liu, Chem. Sci.
bromination aromatization of chiral cyclohexanone derivatives.
A variety of chiral phenol derivatives were obtained in good
yields and high to excellent enantioselectivities. Further
investigations into the mechanism of this transformation and
its application to other organic synthetic reactions are
currently underway in our laboratory.
2
015, 6 , 4674.
6
(a) D. Rondon, B. Chaudret, X. D. He, C. S. Labroue, J. Am.
Chem. Soc. 1991, 113, 5671; (b) C. S. Yi, D. W. Lee,
Organometallics 2009, 28, 947.
Acknowledgements
Financially supported by the Zhejiang Natural Science
Foundation (LY15B020005) and the Foundation of Public
Projects of Zhejiang Province (2014C31144), Zhejiang Key
Laboratory of Green Pesticides and Cleaner Production
Technology.
7
8
9
X. J. Jin, K. Taniguchi, K. Yamaguchi, N. Mizuno, Chem. Sci.
2
016, 7 , 5371.
M. Gupta, C. Hagen, R. J. Flesher, W. C. Kaska, C. M. Jensen,
Chem. Commun. 1996, 2083.
(a) D. Bondon, Y. Pietrasanta, B. Pucci, Tetrahedron Lett.
1
977, 18, 821; (b) Moriuchi, T.; Kikushima, K.; Kajikawa, T.;
Hirao. T. Tetrahedron Lett. 2009, 50, 7385; (c) K. Kikushima,
Y.Nishina, RSC Adv. 2013, , 20150-20156; (d) H. C. Tong, K. R.
Reddy, S. T. Liu, Eur. J. Org. Chem. 2014, 3256.
New York, 1996; (b) J. K. Batra, L. Jurd, E. Hamel, Mol. Pharm. 10 For selected recent reviews of the cooperative catalysis, see:
Notes and references
3
1
(a) J. H. P. Tyman, Synthetic and Natural Phenols, Elsevier,
1
985, 27, 94; (c) Z. Getahun, L. Jurd, P. S. Chu, C. M. Lin, E.
Hamel, J. med. Chem. 1992, 35, 1058; (d) P. Abrams, R.
Freeman, C. Anderatröm, A. Mattiasson, Br. J. Urol. 1998, 81
01; (e) V. Arnaudinaud, B. Nay, S. Vergé, A. Nuhrich, G.
(a) Z. H. Shao, H. B. Zhang, Chem. Soc. Rev. 2009, 38, 2745; (b)
C. Zhong, X. D. Shi, Eur. J. Org. Chem. 2010, 2999; (c) A. E.
Allen, D. W. C. MacMillan, Chem. Sci. 2012, 3, 633; (d) Z. T. Du,
Z. H. Shao, Chem. Soc. Rev. 2013, 42, 1337; (e) M. Á.
Fernández-Ibañez, B. Maciá, D. A. Alonso, I. M. Pastor,
Molecules 2013, 18, 10108; (f) D. F. Chen, Z. Y. Han, X. L. Zhou,
L. Z. Gong, Acc. Chem. Res. 2014, 47, 2365; (g) S. M. Inamdar,
V. S. Shinde, N. T. Patil, Org. Biomol. Chem. 2015, 13, 8116.
,
8
Deffieux, J. M. Mérillon, J. P. Monti, J. Vercauteren,
Tetrahedron Lett. 2001, 42, 5669; (f) S. Sawadjoon, P.
Kittakoop, K. Kirtikara, V. Vichai, M. Tanticharoen, Y. J.
Thebtaranonth, Org. Chem. 2002, 67, 5470; (g) G. Shen, B. S.
Blagg, J. Org. Lett. 2005,
Musa, S. Tamir, T. Peter, J. Vaya, J. Med. Chem. 2007, 50
676; (i) N. Sekine, T. Ashitani, T. Murayama, S. Shibutani, S.
Hattori, K. Takahashi, J. Agric. Food. Chem. 2009, 57, 5707.
(a) O. Krull, B. Wünsch, Bioorg. Med. Chem. 2004, 12, 1439;
7, 2157; (h) S. Khatib, O. Nerya, R. 11 For examples of Cu-catalyzed reactions, see: a) T. Yang, A.
,
Ferrali, L. Campbell, D. J. Dixon, Chem. Commun. 2008, 2923;
(b) J. Xie, Z. Z. Huang, Chem. Commun. 2010, 46, 1947; (c) E.
Gómez-Bengoa, J. M. García, Z. Jiménez, I. Lapuerta, A.
Mielgo, J. M. Odriozola, I. Otazo, J. Razkin, I. Urruzuno, S.
2
2
(
b) S. Brandes, M. Bella, A. Kjaersgaard, K. A. Jørgensen,
Vera, M. Oiarbide, C. Palomo, Chem. Sci. 2013, 4, 3198; For
Angew. Chem. 2006, 118, 1165; Angew. Chem. Int. Ed. 2006,
45, 1147; (c) T. Y. Liu, H. Cui, Q. Chai, J. Long, B. J. Li, Y. Wu.; L.
representative examples of Pd-catalyzed reactions, see: (d) G.
L. Zhao, F. Ullah, L. Deiana, S. Z. Lin, Q. Zhang, J. L. Sun, I.
Ibrahem, P. Dziedzic, A. Córdova. Chem. Eur. J. 2010, 16, 1585;
(e) W. S. Sun, G. M. Zhu, L. Hong, R. Wang, Chem. Eur. J. 2011,
17, 13958; (f) M. L. Li, S. Datta, D. M. Barber, D. J. Dixon, Org.
Lett. 2012, 14, 6350; (g) M. Yoshida, T. Terumine, E. Masaki, S.
Hara, J. Org. Chem. 2013, 78, 10853; (h) S. Tang, X. D. Wu, W.
S. Ding, Chem. Commun. 2007, 2228; (d) H. S. P. Rao, K.
Geetha, Tetrahedron Lett. 2009, 50, 3836; (e) M. J. Mphahlele,
Molecules 2009, 14, 5308; (f)H. Zhang, Y. H. Liao, W. C. Yuan,
X. M. Zhang, Eur. J. Org. Chem. 2010, 3215; (g) Y. Sohtome, B.
Shin, N. Horitsugi, R. Takagi, K. Noguchi, K. Nagasawa, Angew.
Chem. 2010, 122, 7457; Angew. Chem. Int. Ed
.
2010, 49, 7299;
Q. Liao, K. Liu, C. Liu, S. Z. Luo, A. W. Lei, Org. Lett. 2014, 16,
(
h) H. S. P. Rao, K. Geetha, M. Kamalraj, Tetrahedron 2011, 67
,
3584; (i) H. Zhou, L. Zhang, C. M. Xu, S. Z. Luo, Angew. Chem.
2015, 127, 12836; Angew. Chem. Int. Ed. 2015, 54, 12645; (j)
A. S. Marques, M. Giardinetti, J. Marrot, V. Coeffard, X.
Moreau, C. Greck, Org. Biomol. Chem. 2016, 14, 2828; (k) K. S.
Halskov, L. Næsborg, F. Tur, K. A. Jørgensen, Org. Lett. 2016,
18, 2220; (l) L. A. Leth, F. Glaus, M. Mezza, L. Fu, M. K.
Thøgersen, E. A. Bitsch, K. A. Jørgensen, Angew. Chem. 2016,
128, 15498; Angew. Chem. Int. Ed. 2016, 55, 15272; (m) L.
Næsborg, F. Tur, M. Meazza, J. Blom, K. S. Halskov, K. A.
Jørgensen, Chem. Eur. J. 2017, 23, 268; For examples of Au-
catalyzed reactions, see: (n) M. Chiarucci, M. D. Lillo, A.
Romaniello, P. G. Cozzi, G. Cera, M. Bandini, Chem. Sci. 2012,
8
6
7
4
146; (i) Y. Liu, M. P. Doyle, Org. Biomol. Chem. 2012, 10
388; (j) S. C. Lu, P. Zheng, G. Liu, J. Org. Chem. 2012, 77
,
,
711; (k) M. T. Keβler, M. H. G. Prechtl, ChemCatChem 2012,
, 326; (l)M. Montesinos-magraner, C. Vila, G. Blay, I.
Fernandez, M. C. Munoz, J. R. Pedro, Adv. Synth. Catal. 2015,
57, 3047.
3
3
(a) P. P. Fu, R. G. Harvey, Chem. Rev. 1978, 78, 317; (b) P.
Bamfield, P. F. Gordon, Chem. Soc. Rev. 1984, 13, 441; (c) J.
Muzart, Eur. J. Org. Chem. 2010, 3779; (d) J. Choi, A. H. R.
MacArthur, M. Brookhart, A. S. Goldman, Chem. Rev. 2011,
1
11, 1761; (e)S. A. Girard, H. W. Huang, F. Zhou, G. J. Deng, C.
J. Li, Org. Chem. Front. 2015, , 279; (f) Y. F. Liang, X. Y. Li, X.
2
3, 2859; (o) A. Ballesteros, P. Morán-Poladura, J. M. González,
Y. Wang, M. C. Zou, C. H. Tang, Y. J. Liang, S. Song, N. Jiao, J.
Am. Chem. Soc. 2016, 138 , 12271.
Chem. Commun. 2016, 52, 2905; For examples of Iridium-
catalyzed reaction, see: (p) S. Krautwald, M. A. Schafroth, D.
4
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Organic & Biomolecular Chemistry
Journal Name
COMMUNICATION
Sarlah, E. M. Carreira, J. Am. Chem. Soc. 2014, 136, 3020; (q)
B. Bhaskararao, R. B. Sunoj, J. Am. Chem. Soc. 2015, 137
5712; For examples of Rhodium-catalyzed reaction, see: (r) J.
View Article Online
DOI: 10.1039/C7OB01114H
,
1
Gong, K. Li, S. Qurban, Q. Kang, Chin. J. Chem. 2016, 34, 1225;
s) F. A. Cruz, V. M. Dong, J. Am. Chem. Soc. 2017, 139, 1029;
For other metal catalysts, see: (t) Z. H. Xu, L. Liu, K. Wheeler,
H. Wang, Angew. Chem. 2011, 123, 3546; Angew. Chem. Int.
Ed. 2011, 50, 3484; (u) L. Liu, R. Sarkisian, Z. H. Xu, H. Wang, J.
Org. Chem. 2012, 77, 7693.
1
2 (a) D. Q. Xu, A. B. Xia, S. P. Luo, J. Tang, S. Zhang, J. R. Jiang, Z.
Y. Xu, Angew. Chem. 2009, 121, 3879; Angew. Chem. Int. Ed.
2
009, 48, 3821; (b) A. B. Xia, C. Wu, D. Q. Xu, Y. F. Wang, X. H.
Du, Z. B. Li, Z. Y. Xu, J. Org. Chem. 2013, 78, 1254; (c) A. B. Xia,
C. Wu, T. Wang, Y. P. Zhang, X. H. Du, A. G. Zhong, D. Q. Xu, Z.
Y. Xu, Adv. Synth. Catal. 2014, 356, 1753.
1
1
3 For more details, please see the Supporting Information.
4 For selected reviews, see: (a) X. C. Li, D. Ferreira, Y. Ding,
Curr. Org. Chem. 2010, 14, 1678; (b) J. Autschbach, L. Nitsch-
Velasquez, M. Rudolph, Top. Curr. Chem. 2010, 1. For
selected examples of the use of this technique to assign the
absolute configurations of chiral organic molecules, see: (c) F.
Furche, R. Ahlrichs, C. Wachsmann, E. Weber, A. Sobanski, F.
Vögtle, S. Grimme, J. Am. Chem. Soc. 2000, 122, 1717; (d) C.
Diedrich, S. Grimme, J. Phys. Chem. A, 2003, 107, 2524; (e) M.
Kim, D. Won, J. Han, Bioorg. Med. Chem. Lett. 2010, 20, 4337;
(f) A. B. Xia, L. Zhao, T. Wang, Y. P. Zhang, A. G. Zhong, D. Q.
Xu, Z. Y. Xu, New J. Chem. 2015, 39, 355.
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