Phosphine Oxide-Sc(OTf)3 Catalyzed Highly Regio- and Enantioselective Bromoaminocyclization of (E)-Cinnamyl Tosylcarbamates. An Approach to a Class of Synthetically Versatile Functionalized Molecules

Article abstract of DOI:10.1021/acs.orglett.5b03459

A highly regio- and enantioselective bromoaminocyclization of (E)-cinnamyl tosylcarbamates catalyzed by a chiral phosphine oxide-Sc(OTf)₃ complex is described. A wide variety of optically active aryl 5-bromo-1,3-oxazinan-2-ones can be obtained

Full text of DOI:10.1021/acs.orglett.5b03459

Letter
pubs.acs.org/OrgLett
Phosphine Oxide−Sc(OTf)3 Catalyzed Highly Regio- and
Enantioselective Bromoaminocyclization of (E)‑Cinnamyl
Tosylcarbamates. An Approach to a Class of Synthetically Versatile
Functionalized Molecules
Hongjie Pan,† Hu Huang,† Weigang Liu,† Hua Tian,† and Yian Shi*,†,‡
†Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of
Chemistry, Chinese Academy of Sciences, Beijing 100190, China
‡Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, United States
S
* Supporting Information
ABSTRACT: A highly regio- and enantioselective bromoaminocyc-
lization of (E)-cinnamyl tosylcarbamates catalyzed by a chiral
phosphine oxide−Sc(OTf)3 complex is described. A wide variety of
optically active aryl 5-bromo-1,3-oxazinan-2-ones can be obtained
with high yield and enantioselectivity.
Scheme 2
Scheme 3
symmetric halogenation of olefins provides an effective
A
approach to stereoselectively introduce two heteroatoms
onto C−C double bonds (Scheme 1)1 and has been an active
Scheme 1. Catalytic Asymmetric Halogenation of Olefins
research area in recent years. Various effective catalytic systems,
including a chiral Lewis acid,2,3 chiral base,4,5 and chiral
phosphoric acid or phosphate,6,7 have been developed.
Developing catalytic systems with a broad substrate scope and
great synthetic versatility is still highly desirable. In our own
studies, we have shown that the complex of Sc(OTf)3 with chiral
phosphine L1 (Trost ligand8) or chiral phosphine oxide L2
(Figure 1) is a highly effective catalyst for asymmetric
Our initial studies were carried out with cinnamyl
tosylcarbamate (3a) as a test substrate and 1,3-dibromo-5,5-
dimethylhydantoin (DBDMH) as the bromine source. Treating
3a with DBDMH and 5 mol % Sc(OTf)3−L1 in CHCl3 at −50
°C led to 5-bromo-1,3-oxazinan-2-one 4a in 57% yield and 85%
ee (Table 1, entry 1). A higher ee (95%) was obtained when
phosphine oxide L2 was used as the ligand (Table 1, entry 2).
Various reaction conditions were subsequently examined with
L2. No desired product 4a was obtained with N-bromosuccini-
mide (NBS), CH3CONHBr, PhCONHBr, and 2,4,4,6-tetra-
bromo-2,5-cyclohexadienone (TBCO) (Table 1, entries 3−6).
Among the solvents examined, CHCl3 gave the best results
(Table 1, entries 2, 7−10). Various additives were also
investigated (Table 1, entries 11−15).9b When the reaction
was carried out in the presence of 1.2 equiv of NaCl, compound
4a was isolated in 83% yield and 96% ee (Table 1, entry 12). A
lower yield and ee were obtained with L1 under similar reaction
conditions (Table 1, entry 16). A slightly higher yield was
obtained when the catalyst loading was decreased to 2 mol %
Figure 1. Selected examples of chiral ligands examined.
bromocyclization of (Z)-allyl N-tosylcarbamates (1) (Scheme
2)9a and 2,4-dienyl N-tosylcarbamates.9b In our efforts to further
expand the reaction scope, we have found that (E)-cinnamyl
tosylcarbamates (3) are highly effective substrates for the
asymmetric 6-endo-bromoaminocyclization with the chiral Sc-
(OTf)3 catalyst (Scheme 3). Herein, we wish to report our
preliminary efforts on this subject.
Received: December 4, 2015
© XXXX American Chemical Society
A
DOI: 10.1021/acs.orglett.5b03459
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
a
Table 1. Studies on the Reaction Conditions
Scheme 4. Enantioselective Bromoaminocyclization of (E)-
Cinnamyl Tosylcarbamates
a
b
c
entry
L
Br source
DBDMH
solvent
additive yield (%) ee (%)
1
L1
L2
L2
L2
L2
L2
L2
L2
L2
L2
L2
L2
L2
L2
L2
L1
L2
−
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CH2Cl2
THF
−
−
−
57
48
−
85
95
−
2
DBDMH
NBS
3
4
CH3CONHBr
PhCONHBr
TBCO
−
−
−
5
−
−
−
6
−
−
−
7
DBDMH
DBDMH
DBDMH
DBDMH
DBDMH
DBDMH
DBDMH
DBDMH
DBDMH
DBDMH
DBDMH
DBDMH
DBDMH
−
42
83
8
−
−
−
9
PhMe
−
−
−
10
11
12
13
14
15
16
EtOAc
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
−
−
−
LiCl
NaCl
KCl
NaBr
NaI
NaCl
NaCl
NaCl
NaCl
12
83
78
63
56
59
88
−
65
96
96
84
76
87
96
−
d
17
18
e
19
L2
38
0
a
The reactions were carried out with substrate 3a (0.20 mmol), Br
source (0.24 mmol), additive (0.24 mmol), and Sc(OTf)3−L (1:1)
(0.010 mmol) in CHCl3 (2.0 mL) for 18 h unless otherwise stated.
DBDMH = 1,3-dibromo-5,5-dimethylhydantoin; NBS = N-bromo-
b
succinimide; TBCO = 2,4,4,6-tetrabromo-2,5-cyclohexadienone. Iso-
c
d
lated yield. Determined by chiral HPLC analysis. With Sc(OTf)3−L
e
(1:1) (0.004 mmol). Without Sc(OTf)3.
(Table 1, entry 17). Control experiments showed that both
Sc(OTf)3 and the ligand were important for the reaction. No
product 4a was detected when the reaction was carried out with
Sc(OTf)3 alone (Table 1, entry 18). A racemate was isolated in
38% yield with L2 alone (Table 1, entry 19).
With the optimized reaction conditions in hand, the substrate
scope was subsequently explored. As shown in Scheme 4, a wide
variety of (E)-cinnamyl tosylcarbamates can be bromocyclized to
the corresponding 5-bromo-1,3-oxazinan-2-ones 4 in 65−96%
yield and 87−99% ee (the X-ray structure of 4a is shown in
Figure 2). The aryl groups can be ortho- (Scheme 4, 4b and 4c),
meta- (Scheme 4, 4d−4f), and para-substituted (Scheme 4, 4g−
4k). The di- and trisubstituted substrates are also highly effective
for the reaction (Scheme 4, 4l−4o). The aryl groups can be other
aromatics such as naphthalene and thiophene (Scheme 4, 4p, 4q,
and 4r). In all these cases, the bromoaminocyclization proceeded
with high regioselectivity, and essentially only 6-endo products
were obtained. When (Z)-cinnamyl tosylcarbamate (3s) was
subjected to the reaction conditions, oxazolidinone 4s was
isolated in 20% yield and 48% ee (Scheme 5).
a
The reactions were carried out with substrate 3 (0.50 mmol),
Sc(OTf)3−L2 (1:1) (0.010 mmol), DBDMH (0.60 mmol), and NaCl
(0.60 mmol) in CHCl3 (5.0 mL) at −50 °C for 18 h. The yield was the
isolated yield based on 3. The absolute configurations of 4a, 4k, and
4n were assigned based on their X-ray structures. The absolute
configurations of the others were tentatively proposed by analogy.
The reaction can also be carried out on a relatively larger scale.
As shown in Scheme 6, 3.20 g of 5-bromo-1,3-oxazinan-2-one 4a
was obtained in 78% yield with 99% ee after recrystallization.
Compound 4a can serve as a versatile chiral synthetic
intermediate for further transformations (Scheme 7). Treating
4a with LiAlH4 or DIBAL-H led to compounds 5a and 6a in 74%
and 68% yield, respectively. When 4a was treated with KOH−
H2O or K2CO3−MeOH, compounds 7a and 8a were obtained in
86% and 90% yield, respectively. These two compounds were
Figure 2. X-ray structure of compound 4a.
likely formed via aziridine intermediate 9a. This is supported by
the fact that aziridine 9a, obtained from 6a with K2CO3−
MeCN,10 can be converted to 8a with K2CO3−MeOH in 87%
yield. Azide 10a can be obtained from 6a in 86% yield with
TMSN3 and TBAF (Scheme 8) (for the X-ray structure of 10a,
B
DOI: 10.1021/acs.orglett.5b03459
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
reaction mechanism, expanding the substrate scope, and
developing more effective catalytic systems.
Scheme 5. Bromoaminocyclization of (Z)-Cinnamyl
Tosylcarbamate
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.orglett.5b03459.
Experimental procedures, characterizations, X-ray struc-
tures, HPLC data for the determination of enantiomeric
excess, and NMR spectra (PDF)
Crystallographic data for 4a (CIF)
Crystallographic data for 4k (CIF)
Crystallographic data for 4n (CIF)
Crystallographic data for 5a (CIF)
Crystallographic data for 6a (CIF)
Crystallographic data for 7a (CIF)
Scheme 6. Bromoaminocyclization on a Gram Scale
Scheme 7. Synthetic Transformations of Bromide 4a
Crystallographic data for 10a (CIF)
Crystallographic data for 12a (CIF)
AUTHOR INFORMATION
Corresponding Author
■
*E-mail: Yian.Shi@colostate.edu.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We gratefully acknowledge the National Basic Research Program
of China (973 program, 2011CB808600), the National Natural
Science Foundation of China (21172221), and the Chinese
Academy of Sciences for the financial support.
Scheme 8. Synthetic Transformation of Bromoaminoalcohol
6a
REFERENCES
■
(1) For leading reviews of olefin halogenation, see: (a) Dowle, M. D.;
Davies, D. I. Chem. Soc. Rev. 1979, 8, 171. (b) Li, G.; Kotti, S. R. S. S.;
Timmons, C. Eur. J. Org. Chem. 2007, 2007, 2745. (c) Chen, G.; Ma, S.
Angew. Chem., Int. Ed. 2010, 49, 8306. (d) Castellanos, A.; Fletcher, S. P.
Chem. - Eur. J. 2011, 17, 5766. (e) Tan, C. K.; Zhou, L.; Yeung, Y.-Y.
Synlett 2011, 2011, 1335. (f) Hennecke, U. Chem. - Asian J. 2012, 7, 456.
(g) Denmark, S. E.; Kuester, W. E.; Burk, M. T. Angew. Chem., Int. Ed.
2012, 51, 10938. (h) Murai, K.; Fujioka, H. Heterocycles 2013, 87, 763.
(i) Chemler, S. R.; Bovino, M. T. ACS Catal. 2013, 3, 1076. (j) Tan, C.
K.; Yeung, Y.-Y. Chem. Commun. 2013, 49, 7985. (k) Tripathi, C. B.;
Mukherjee, S. Synlett 2014, 25, 163. (l) Cheng, Y. A.; Yu, W. Z.; Yeung,
Y.-Y. Org. Biomol. Chem. 2014, 12, 2333. (m) Chen, J.; Zhou, L. Synthesis
2014, 46, 586. (n) Zheng, S.; Schienebeck, C. M.; Zhang, W.; Wang, H.-
Y.; Tang, W. Asian J. Org. Chem. 2014, 3, 366.
see Supporting Information).10 A new C−C bond can also be
stereoselectively formed from the C−Br bond. For example,
compound 11a was isolated in 89% yield when 4a was reacted
with allyltributyltin and AIBN at 85 °C (Scheme 9).11 In all these
transformations, the optical purity was maintained.
Scheme 9. Synthetic Transformation of Bromide 4a
(2) For leading references on Lewis acid catalyzed intramolecular
enantioselective halogenation of olefins, see: (a) Inoue, T.; Kitagawa,
O.; Ochiai, O.; Shiro, M.; Taguchi, T. Tetrahedron Lett. 1995, 36, 9333.
(b) Inoue, T.; Kitagawa, O.; Saito, A.; Taguchi, T. J. Org. Chem. 1997, 62,
7384. (c) Kang, S. H.; Lee, S. B.; Park, C. M. J. Am. Chem. Soc. 2003, 125,
15748. (d) Kwon, H. Y.; Park, C. M.; Lee, S. B.; Youn, J.-H.; Kang, S. H.
Chem. - Eur. J. 2008, 14, 1023. (e) Ning, Z.; Jin, R.; Ding, J.; Gao, L.
Synlett 2009, 2009, 2291. (f) Miles, D. H.; Veguillas, M.; Toste, F. D.
Chem. Sci. 2013, 4, 3427. (g) Filippova, L.; Stenstrøm, Y.; Hansen, T. V.
Tetrahedron Lett. 2014, 55, 419. (h) Arai, T.; Sugiyama, N.; Masu, H.;
Kado, S.; Yabe, S.; Yamanaka, M. Chem. Commun. 2014, 50, 8287.
(i) Zhu, C.-L.; Tian, J.-S.; Gu, Z.-Y.; Xing, G.-W.; Xu, H. Chem. Sci. 2015,
6, 3044. (j) Cai, Y.; Zhou, P.; Liu, X.; Zhao, J.; Lin, L.; Feng, X. Chem. -
Eur. J. 2015, 21, 6386. (k) Arai, T.; Watanabe, O.; Yabe, S.; Yamanaka,
M. Angew. Chem., Int. Ed. 2015, 54, 12767.
In summary, we have developed a highly regio- and
enantioselective bromoaminocyclization process for (E)-cin-
namyl tosylcarbamates with DBDMH as the bromine source and
chiral phosphine oxide−Sc(OTf)3 complex as the catalyst. A
wide of optically active aryl 5-bromo-1,3-oxazinan-2-ones have
been obtained in 65−96% yield and 87−99% ee. The reaction
can be performed on a gram scale. The resulting halides have
been shown to be highly versatile synthetic intermediates and can
be further transformed into various useful functionalized
molecules. Further efforts will be devoted to understanding the
(3) For leading references on Lewis acid catalyzed intermolecular
enantioselective halogenation of olefins, see: (a) Li, G.; Wei, H.-X.; Kim,
S. H. Tetrahedron 2001, 57, 8407. (b) Cai, Y.; Liu, X.; Hui, Y.; Jiang, J.;
C
DOI: 10.1021/acs.orglett.5b03459
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Wang, W.; Chen, W.; Lin, L.; Feng, X. Angew. Chem., Int. Ed. 2010, 49,
6160. (c) Cai, Y.; Liu, X.; Jiang, J.; Chen, W.; Lin, L.; Feng, X. J. Am.
Chem. Soc. 2011, 133, 5636. (d) Cai, Y.; Liu, X.; Li, J.; Chen, W.; Wang,
W.; Lin, L.; Feng, X. Chem. - Eur. J. 2011, 17, 14916. (e) Cai, Y.; Liu, X.;
Zhou, P.; Kuang, Y.; Lin, L.; Feng, X. Chem. Commun. 2013, 49, 8054.
(f) Hu, D. X.; Shibuya, G. M.; Burns, N. Z. J. Am. Chem. Soc. 2013, 135,
12960. (g) Hu, D. X.; Seidl, F. J.; Bucher, C.; Burns, N. Z. J. Am. Chem.
Soc. 2015, 137, 3795.
Sawamura, Y.; Sakakura, A.; Ishihara, K. Angew. Chem., Int. Ed. 2014, 53,
6974. (au) Yin, Q.; You, S.-L. Org. Lett. 2014, 16, 1810. (av) Yin, Q.;
You, S.-L. Org. Lett. 2014, 16, 2426. (aw) Jaganathan, A.; Borhan, B. Org.
Lett. 2014, 16, 3616. (ax) Ke, Z.; Tan, C. K.; Chen, F.; Yeung, Y.-Y. J. Am.
Chem. Soc. 2014, 136, 5627. (ay) Wilking, M.; Daniliuc, C. G.;
Hennecke, U. Synlett 2014, 25, 1701. (az) Tripathi, C. B.; Mukherjee, S.
Org. Lett. 2014, 16, 3368. (ba) Murai, K.; Shimizu, N.; Fujioka, H. Chem.
Commun. 2014, 50, 12530. (bb) Murai, K.; Nakajima, J.; Nakamura, A.;
Hyogo, N.; Fujioka, H. Chem. - Asian J. 2014, 9, 3511. (bc) Mizar, P.;
(4) For leading references on chiral base catalyzed intramolecular
enantioselective halogenation of olefins, see: (a) Wang, M.; Gao, L. X.;
Mai, W. P.; Xia, A. X.; Wang, F.; Zhang, S. B. J. Org. Chem. 2004, 69,
2874. (b) Sakakura, A.; Ukai, A.; Ishihara, K. Nature 2007, 445, 900.
(c) Whitehead, D. C.; Yousefi, R.; Jaganathan, A.; Borhan, B. J. Am.
Chem. Soc. 2010, 132, 3298. (d) Zhang, W.; Zheng, S.; Liu, N.; Werness,
J. B.; Guzei, I. A.; Tang, W. J. Am. Chem. Soc. 2010, 132, 3664. (e) Veitch,
G. E.; Jacobsen, E. N. Angew. Chem., Int. Ed. 2010, 49, 7332. (f) Murai,
K.; Matsushita, T.; Nakamura, A.; Fukushima, S.; Shimura, M.; Fujioka,
H. Angew. Chem., Int. Ed. 2010, 49, 9174. (g) Zhou, L.; Tan, C. K.; Jiang,
X.; Chen, F.; Yeung, Y.-Y. J. Am. Chem. Soc. 2010, 132, 15474.
(h) Jaganathan, A.; Garzan, A.; Whitehead, D. C.; Staples, R. J.; Borhan,
B. Angew. Chem., Int. Ed. 2011, 50, 2593. (i) Yousefi, R.; Whitehead, D.
C.; Mueller, J. M.; Staples, R. J.; Borhan, B. Org. Lett. 2011, 13, 608.
(j) Liu, N.; Werness, J. B.; Guzei, I. A.; Tang, W. Tetrahedron 2011, 67,
4385. (k) Zhou, L.; Chen, J.; Tan, C. K.; Yeung, Y.-Y. J. Am. Chem. Soc.
2011, 133, 9164. (l) Chen, Z.-M.; Zhang, Q.-W.; Chen, Z.-H.; Li, H.; Tu,
Y.-Q.; Zhang, F.-M.; Tian, J.-M. J. Am. Chem. Soc. 2011, 133, 8818.
(m) Tan, C. K.; Zhou, L.; Yeung, Y.-Y. Org. Lett. 2011, 13, 2738.
(n) Lozano, O.; Blessley, G.; Campo, T. M. D.; Thompson, A. L.;
Giuffredi, G. T.; Bettati, M.; Walker, M.; Borman, R.; Gouverneur, V.
Angew. Chem., Int. Ed. 2011, 50, 8105. (o) Li, H.; Zhang, F.-M.; Tu, Y.-
Q.; Zhang, Q.-W.; Chen, Z.-M.; Chen, Z.-H.; Li, J. Chem. Sci. 2011, 2,
1839. (p) Tan, C. K.; Chen, F.; Yeung, Y.-Y. Tetrahedron Lett. 2011, 52,
Burrelli, A.; Gunther, E.; Softje, M.; Farooq, U.; Wirth, T. Chem. - Eur. J.
̈
̈
2014, 20, 13113. (bd) Toda, Y.; Pink, M.; Johnston, J. N. J. Am. Chem.
Soc. 2014, 136, 14734. (be) Kawato, Y.; Kubota, A.; Ono, H.; Egami, H.;
Hamashima, Y. Org. Lett. 2015, 17, 1244. (bf) Cheng, Y. A.; Yu, W. Z.;
Yeung, Y.-Y. Angew. Chem., Int. Ed. 2015, 54, 12102. (bg) Tripathi, C. B.;
Mukherjee, S. Org. Lett. 2015, 17, 4424.
(5) For leading references on chiral base catalyzed intermolecular
enantioselective halogenation of olefins, see: (a) Nicolaou, K. C.;
Simmons, N. L.; Ying, Y.; Heretsch, P. M.; Chen, J. S. J. Am. Chem. Soc.
2011, 133, 8134. (b) Zhang, W.; Liu, N.; Schienebeck, C. M.; Zhou, X.;
Izhar, I. I.; Guzei, I. A.; Tang, W. Chem. Sci. 2013, 4, 2652. (c) Zhang, Y.;
Xing, H.; Xie, W.; Wan, X.; Lai, Y.; Ma, D. Adv. Synth. Catal. 2013, 355,
68. (d) Li, L.; Su, C.; Liu, X.; Tian, H.; Shi, Y. Org. Lett. 2014, 16, 3728.
(e) Qi, J.; Fan, G.-T.; Chen, J.; Sun, M.-H.; Dong, Y.-T.; Zhou, L. Chem.
Commun. 2014, 50, 13841. (f) Zhang, X.; Li, J.; Tian, H.; Shi, Y. Chem. -
Eur. J. 2015, 21, 11658. (g) Soltanzadeh, B.; Jaganathan, A.; Staples, R. J.;
Borhan, B. Angew. Chem., Int. Ed. 2015, 54, 9517.
(6) For leading references on chiral phosphoric acid and phosphate
catalyzed intramolecular enantioselective halogenation of olefins, see:
(a) Hennecke, U.; Muller, C. H.; Frohlich, R. Org. Lett. 2011, 13, 860.
̈
̈
(b) Rauniyar, V.; Lackner, A. D.; Hamilton, G. L.; Toste, F. D. Science
2011, 334, 1681. (c) Huang, D.; Wang, H.; Xue, F.; Guan, H.; Li, L.;
Peng, X.; Shi, Y. Org. Lett. 2011, 13, 6350. (d) Denmark, S. E.; Burk, M.
T. Org. Lett. 2012, 14, 256. (e) Wang, Y.-M.; Wu, J.; Hoong, C.;
Rauniyar, V.; Toste, F. D. J. Am. Chem. Soc. 2012, 134, 12928.
4892. (q) Muller, C. H.; Wilking, M.; Ruhlmann, A.; Wibbeling, B.;
̈
̈
Hennecke, U. Synlett 2011, 2011, 2043. (r) Chen, J.; Zhou, L.; Tan, C.
K.; Yeung, Y.-Y. J. Org. Chem. 2012, 77, 999. (s) Zhang, W.; Liu, N.;
Schienebeck, C. M.; Decloux, K.; Zheng, S.; Werness, J. B.; Tang, W.
Chem. - Eur. J. 2012, 18, 7296. (t) Dobish, M. C.; Johnston, J. N. J. Am.
Chem. Soc. 2012, 134, 6068. (u) Chen, J.; Zhou, L.; Yeung, Y.-Y. Org.
Biomol. Chem. 2012, 10, 3808. (v) Murai, K.; Nakamura, A.; Matsushita,
T.; Shimura, M.; Fujioka, H. Chem. - Eur. J. 2012, 18, 8448. (w) Jiang, X.;
Tan, C. K.; Zhou, L.; Yeung, Y.-Y. Angew. Chem., Int. Ed. 2012, 51, 7771.
(x) Paull, D. H.; Fang, C.; Donald, J. R.; Pansick, A. D.; Martin, S. F. J.
Am. Chem. Soc. 2012, 134, 11128. (y) Tungen, J. E.; Nolsøe, J. M. J.;
Hansen, T. V. Org. Lett. 2012, 14, 5884. (z) Ikeuchi, K.; Ido, S.;
Yoshimura, S.; Asakawa, T.; Inai, M.; Hamashima, Y.; Kan, T. Org. Lett.
2012, 14, 6016. (aa) Fang, C.; Paull, D. H.; Hethcox, J. C.; Shugrue, C.
R.; Martin, S. F. Org. Lett. 2012, 14, 6290. (ab) Zhou, L.; Tay, D. W.;
Chen, J.; Leung, G. Y. C.; Yeung, Y.-Y. Chem. Commun. 2013, 49, 4412.
(ac) Chen, F.; Tan, C. K.; Yeung, Y.-Y. J. Am. Chem. Soc. 2013, 135,
1232. (ad) Zeng, X.; Miao, C.; Wang, S.; Xia, C.; Sun, W. Chem.
Commun. 2013, 49, 2418. (ae) Garzan, A.; Jaganathan, A.; Marzijarani,
N. S.; Yousefi, R.; Whitehead, D. C.; Jackson, J. E.; Borhan, B. Chem. -
Eur. J. 2013, 19, 9015. (af) Brindle, C. S.; Yeung, C. S.; Jacobsen, E. N.
(f) Romanov-Michailidis, F.; Guen
Ed. 2013, 52, 9266. (g) Romanov-Michailidis, F.; Guen
A. Org. Lett. 2013, 15, 5890. (h) Xie, W.; Jiang, G.; Liu, H.; Hu, J.; Pan,
X.; Zhang, H.; Wan, X.; Lai, Y.; Ma, D. Angew. Chem., Int. Ed. 2013, 52,
12924. (i) Liu, H.; Jiang, G.; Pan, X.; Wan, X.; Lai, Y.; Ma, D.; Xie, W.
́
ee
́
, L.; Alexakis, A. Angew. Chem., Int.
ee, L.; Alexakis,
́
́
Org. Lett. 2014, 16, 1908. (j) Muller, C. H.; Rosner, C.; Hennecke, U.
̈
̈
Chem. - Asian J. 2014, 9, 2162. (k) Romanov-Michailidis, F.; Romanova-
Michaelides, M.; Pupier, M.; Alexakis, A. Chem. - Eur. J. 2015, 21, 5561.
(7) For leading references on chiral phosphoric acid and phosphate
catalyzed intermolecular enantioselective halogenation of olefins, see:
(a) Li, G.-X.; Fu, Q.-Q.; Zhang, X.-M.; Jiang, J.; Tang, Z. Tetrahedron:
Asymmetry 2012, 23, 245. (b) Alix, A.; Lalli, C.; Retailleau, P.; Masson,
G. J. Am. Chem. Soc. 2012, 134, 10389. (c) Honjo, T.; Phipps, R. J.;
Rauniyar, V.; Toste, F. D. Angew. Chem., Int. Ed. 2012, 51, 9684.
(8) Trost, B. M.; Van Vranken, D. L.; Bingel, C. J. Am. Chem. Soc. 1992,
114, 9327.
(9) (a) Huang, D.; Liu, X.; Li, L.; Cai, Y.; Liu, W.; Shi, Y. J. Am. Chem.
Soc. 2013, 135, 8101. (b) Huang, H.; Pan, H.; Cai, Y.; Liu, M.; Tian, H.;
Shi, Y. Org. Biomol. Chem. 2015, 13, 3566. (c) Liu, W.; Pan, H.; Tian, H.;
Shi, Y. Org. Lett. 2015, 17, 3956.
(10) Egart, B.; Lentz, D.; Czekelius, C. J. Org. Chem. 2013, 78, 2490.
(11) Hanessian, S.; Vanasse, B.; Yang, H.; Alpegiani, M. Can. J. Chem.
1993, 71, 1407.
Chem. Sci. 2013, 4, 2100. (ag) Wilking, M.; Muck-Lichtenfeld, C.;
̈
Daniliuc, C. G.; Hennecke, U. J. Am. Chem. Soc. 2013, 135, 8133.
(ah) Murai, K.; Matsushita, T.; Nakamura, A.; Hyogo, N.; Nakajima, J.;
Fujioka, H. Org. Lett. 2013, 15, 2526. (ai) Tripathi, C. B.; Mukherjee, S.
Angew. Chem., Int. Ed. 2013, 52, 8450. (aj) Zhao, Y.; Jiang, X.; Yeung, Y.-
Y. Angew. Chem., Int. Ed. 2013, 52, 8597. (ak) Sawamura, Y.; Nakatsuji,
H.; Sakakura, A.; Ishihara, K. Chem. Sci. 2013, 4, 4181. (al) Jaganathan,
A.; Staples, R. J.; Borhan, B. J. Am. Chem. Soc. 2013, 135, 14806.
(am) Yousefi, R.; Ashtekar, K. D.; Whitehead, D. C.; Jackson, J. E.;
Borhan, B. J. Am. Chem. Soc. 2013, 135, 14524. (an) Yin, Q.; You, S.-L.
Org. Lett. 2013, 15, 4266. (ao) Armstrong, A.; Braddock, D. C.; Jones, A.
X.; Clark, S. Tetrahedron Lett. 2013, 54, 7004. (ap) Cai, Q.; Yin, Q.; You,
S.-L. Asian J. Org. Chem. 2014, 3, 408. (aq) Han, X.; Dong, C.; Zhou, H.-
B. Adv. Synth. Catal. 2014, 356, 1275. (ar) Tan, C. K.; Er, J. C.; Yeung, Y.-
Y. Tetrahedron Lett. 2014, 55, 1243. (as) Tay, D. W.; Leung, G. Y. C.;
Yeung, Y.-Y. Angew. Chem., Int. Ed. 2014, 53, 5161. (at) Nakatsuji, H.;
D
DOI: 10.1021/acs.orglett.5b03459
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