Stereoselective synthesis of 2,5-disubstituted pyrrolidines: Via gold-catalysed anti-Markovnikov hydroamination-initiated tandem reactions

Article abstract of DOI:10.1039/c9cc05295j

A series of gold-catalysed intramolecular anti-Markovnikov hydroamination-initiated azidation, allylation and heteroarylation reactions of chiral homopropargyl sulfonamides have been developed. Various enantioenriched 2,5-disubstituted pyrrolidines are obtained in moderate to excellent yields with excellent enantioselectivities and generally high diastereoselectivities.

Full text of DOI:10.1039/c9cc05295j

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Stereoselective synthesis of 2,5-disubstituted pyrrolidines
through gold-catalysed anti-Markovnikov hydroamination-
initiated tandem reactions
Received 00th January 20xx,
Accepted 00th January 20xx
Tong-De Tan,a Yang-Bo Chen,a Ming-Yang Yang,a Jia-Le Wang,a Hao-Ze Su,a Feng-Lin Hong,a Jin-Mei
DOI: 10.1039/x0xx00000x
Zhoua and Long-Wu Ye*ab
www.rsc.org/
addition in terms of terminal alkynes.4,5 By utilizing the ring strain
strategy6 to achieve the anti-Markovnikov regioselectivity, our
group have developed a variety of gold-catalysed intramolecular
alkyne hydroamination initiated oxidation,7a,b dimerization,7c
halogenation,7e and hydrogenation,7f affording diverse chiral five-
membered N-heterocycle skeletons from readily available chiral
A
series of gold-catalysed intramolecular anti-Markovnikov
hydroamination-initiated azidation, allylation and heteroarylation
reactions of chiral homopropargyl sulfonamides have been
developed. Various enantioenriched 2,5-disubstituted pyrrolidines
are obtained in moderate to excellent yields with excellent
enantioselectivities and generally high diastereoselectivities.
homopropargyl sulfonamides by
a chirality-transfer strategy.
However, the external nucleophiles in these cases are still limited to
the weak nucleophiles, such as m-CPBA,7a,b enamide,7c water,7e and
triisopropylsilane.7f Inspired by these results and our recent work
on the Cu-catalysed cascade cyclization of indolyl homopropargyl
amides,8,9 we envisioned that the stronger nucleophiles such as
azidosilanes, allylsilanes and indoles might also trap the iminium
intermediates to afford the corresponding 2,5-disubstituted
pyrrolidines. Of note, previous synthesis of these pyrrolidines
typically starts from the corresponding dihydropyrroles directly or
via lactamol intermediates.10 However, achieving these cascade
cyclizations is highly challenging due to the fact that these external
strong nucleophiles may also attack the alkyne moiety directly.11-13
Pyrrolidine structural motifs, especially the 2,5-disubstituted
pyrrolidines, are present in many bioactive molecules (Figure 1).1 As
a result, a range of synthetic methods have been developed for
their synthesis during the past decade.2 However, successful
examples of enantioselective construction of these functionalized
pyrrolidines remain scarce.3 Therefore, the development of novel
approach for their preparation is highly desirable.
HO
CHCl2
H
O
EtOOC
EtOOC
H
N
COOMe
N
HO
N
HO
OH
antibacterial activity
against S. aureus
inhibition of UGM
pronounced growth activity
F
PG
N
PG
N
NuTMS or NuH
catalyst
[Au]
base (cat.)
PG
HN
O
H
R
Nu
R
N
HOH2C
HO
R
our previous work7d
H
ref. 10
N
NH
1
HOH2C
2 3 4
,
,
N
NH
Ph
OH
PG
N
OH
HO
antineoplastic
R
OH(Me)
anti-chlamydial
infection bioactivity
antitumor
[Au]
NuTMS or NuH
Figure 1 Selected examples of 2,5-disubstituted pyrrolidines in bioactive
molecules.
(this work)
In the past decades, transition-metal-catalysed intramolecular
alkyne hydroamination initiated cascade cyclization has proven to
be an extremely powerful tool for the straightforward synthesis of
various valuable N-heterocycles, but these reactions generally
proceed by an exo-cyclization pathway via a typical Markovnikov
PG
N
PG
N
PG
N
R
N3
R
R
X
2
3
4
 cascade cyclization
 valuable 5-membered N-heterocycles
 excellent enantioselectivities
 generally high diastereoselectivities
a. State Key Laboratory of Physical Chemistry of Solid Surfaces and Key Laboratory
for Chemical Biology of Fujian Province, College of Chemistry and Chemical
Engineering, Xiamen University, Xiamen 361005, China.
Scheme 1 Synthesis of enantioenriched 2,5-disubstituted pyrrolidines 2–4
directly from chiral homopropargyl sulfonamides 1.
E-mail: longwuye@xmu.edu.cn
Herein, we describe the realization of such a gold-catalysed
intramolecular hydroamination-initiated azidation, allylation and
heteroarylation, allowing the direct and efficient synthesis of
various enantioenriched 2,5-disubstituted pyrrolidines from readily
b. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic
Chemistry, Chinese Academy of Sciences, Shanghai 200032, China.
† Electronic supplementary information (ESI) available. CCDC 1937618. For ESI and
crystallographic data in CIF or other electronic format see DOI: 10.1039/
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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available chiral homopropargyl sulfonamides.14-16 Importantly, tolerated (Table 2, entries 3–4). Moreover, a range of aryl-
View Article Online
DOI: 10.1039/C9CC05295J
excellent
enantioselectivities
and
generally
high substituted substrates bearing both electron-donating and electron-
withdrawing groups on the phenyl ring proceeded efficiently to
furnish the desired 2,5-disubstituted pyrrolidines 2e–2l in 65-84%
diastereoselectivities were achieved in these cascade cyclizations.
At the outset, homopropargyl sulfonamide 1a was used as the
model substrate and TMSN3 (2 equiv) as an extermal nucleophilic
reagent for intramolecular hydroamination/azidation reaction. To
our delight, by employing 5 mol % of IPrAuNTf2 as catalyst, the
tandem reaction proceeded smoothly to produce the desired 2-
azido-substituted pyrrolidine 2a in 47% yield (Table 1, entry 1).
Significantly, neither azide–alkyne cycloaddition product11a,b nor
vinyl azide formation11d was observed in this case. Inspired by our
previous results that the use of Et3N as additive might improve the
reaction yield,7d,e further investigations (Table 1, entries 2–5)
revealed that the combination of 1 mol % of Et3N and 6 mol % of
IPrAuNTf2 could lead to the formation of the corresponding
pyrrolidine 2a in 88% yield (Table 1, entry 5). Then, various typical
gold catalysts with a range of electronic and steric characteristics
were screened, but the yield could not be further improved (Table 1,
entries 6–10). Of note, AgNTf2 could also catalyse this reaction to
afford the desired product 2a in 44% yield (Table 1, entry 11) while
the use of copper catalysts failed to give even a trace of 2a.17
yields (Table 2, entries 5–12). Finally, the use of (S)-(+)-tert-
butylsulfinamide-derived homopropargyl sulfonamide 1a′ also
produced the desired azido-substituted pyrrolidine 2a′ with the
opposite enantioselectivity (Table 2, entry 13). Of note, the
enantiomeric excess (ee) was well maintained in these
transformations; we determined the ee of product 2a as a
representative example (Table 2, entry 1). Significantly, high cis
diastereoselectivity could be achieved in all cases (diastereomeric
1
ratio (d.r.) > 10:1, determined by crude H NMR spectroscopy). The
molecular structure of 2j was further confirmed by X-ray
crystallography.18
a
Table 2 Reaction of chiral homopropargyl sulfonamides 1 with TMSN3
PG
NHPG
IPrAuNTf2 (6 mol %)
N
TMSN3
R
N3
Et3N (1 mol %)
DCE, 60 °C, 5 h
R
1
(2 equiv)
2
PG
N
Ts
N
Ts
N
N3
N3
N3
( )
Table 1 Optimization of reaction conditionsa
6
b
TMSN3 (2 equiv)
catalyst (5-10 mol %)
2a
(1) , PG = Ts, 85%, 17:1
2b
Ts
N
Ts
N
Ts
2c,
2d,
65%, 17:1
(3)
75%, 14:1
(4)
HN
( )6
(2) , PG = MBS, 60%, 17:1
N3
( )
( )
+
6
additive, DCE, 60 oC, 5 h
6
Ts
Ts
N
Ts
N
1a
2a
2aa
MeO
N
N3
N3
N3
Yieldb (%)
2e,
2f
2g
(5)
82%, 11:1
(6) , 76%, >20:1
(7) , 84%, >20:1
Ts
Br
Entry Catalyst
Additive
-
2a
2aa 1a
1
IPrAuNTf2 (5 mol %)
47
69
<1
<1
2
7
Ts
N
Ts
F
Cl
N
N
2
IPrAuNTf2 (5 mol %)
IPrAuNTf2 (5 mol %)
IPrAuNTf2 (5 mol %)
IPrAuNTf2 (6 mol %)
Ph3PAuNTf2 (6 mol %)
Et3N (1 mol %)
7
N3
N3
N3
3
Et3N (1.5 mol %) 52
14
24
<1
<1
46
44
75
14
33
2h
2i
2j
(8) , 73%, 17:1
(9) , 74%, >20:1
(10) , 70%, >20:1
4
Et3N (2 mol %)
Et3N (1 mol %)
Et3N (1 mol %)
36
88
70
49
25
12
55
44
3
5
<1
4
Br
Ts
N
Ts
Ts
N
6
N
N3
( )
N3
6
7c
8c
9c,d
10e
11c
CyJohnPhosAuNTf2 (6 mol %) Et3N (1 mol %)
5
N3
BrettPhosAuNTf2 (6 mol %)
Et3N (1 mol %)
Et3N (1 mol %)
Et3N (1 mol %)
-
5
2k
(11) , 66%, 11:1
2l
(12) , 65%, >20:1
2a'
(13) , 84%, 17:1
Ar
(
O)3PAuNTf2 (6 mol %)
2
a Reactions run in vials; [1] = 0.1 M; isolated yields are reported. 99% ee,
determined by HPLC on a chiral stationary phase.
b
Au (III) (6 mol %)
<1
<5
AgNTf2 (10 mol %)
Besides C-N bond formation, this gold-catalysed tandem
reaction was also applicable to C-C bond formation by replacing
azidosilane with allylsilane as a carbon nucleophile. As shown in
a
Reaction conditions: 1a (0.05 mmol), TMSN3 (0.1 mmol), catalyst (5-10
mol %), DCE (0.5 mL), 60 °C, in vials. Measured by 1H NMR using diethyl
b
phthalate as the internal standard. Reaction time: 24 h. d Ar = 2,4-di-tert– Table 3, the treatment of chiral homopropargyl amides 1 with
c
butylphenyl. e Dichloro(2-picolinato)gold(III).
allylsilane (2 equiv) in the presence of IPrAuNTf2 (5 mol %) as
catalyst17 produced the desired 2-allyl-substituted pyrrolidines 3a–
Under the optimized reaction conditions (Table 1, entry 5), the
3l in 80-94% yield with up to 5:1 diastereoselectivity (Table 3,
scope of this gold-catalysed intramolecular hydroamination/
entries 1–12). It should be specially mentioned that the
azidation reaction was then examined (Table 2). A variety of chiral
stereoisomers could be easily separated by column
homopropargyl sulfonamide substrates 1, readily prepared by using
chromatography in all cases. Also, the use of (S)-(+)-tert-
Ellman’s tertbutylsulfinimine chemistry,7 underwent smooth
butylsulfinamide-derived homopropargyl sulfonamide 1a′ delivered
tandem cyclization, leading to the corresponding 2-azide-
the desired allyl-substituted pyrrolidine 3a′ in 90% yield with the
substituted pyrrolidines 2 in mostly high yields. Besides tosyl
opposite enantioselectivity (Table 3, entry 13). Once again, we
protecting group, MBS (p-methoxybenzenesulfonyl) protected
determined the ee value of 3a as a representative example (Table 3,
substrate was also suitable substrate for this reaction, delivering
entry 1), and found that complete chirality transfer was achieved.
the expected product 2b in 60% yield (Table 2, entry 2). In addition,
other alkyl-substituted homopropargyl sulfonamides were also
2 | J. Name., 2012, 00, 1-3
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Table 3 Reaction of chiral homopropargyl sulfonamides 1 with allylsilanea
disubstituted pyrrolidines 2 and 3 is proposed (SchVeiemweArt2ic)l.e OFinrlisnte,
gold-catalysed intramolecular hydroamination of homopropargyl
DOI: 10.1039/C9CC05295J
PG
NHPG
IPrAuNTf2 (5 mol %)
DCE, 60 °C, 3 h
N
sulfonamides 1 via 5-endo-dig cycloisomerization generates the
dihydropyrrole intermediates B, which are then converted into
iminium intermediates C promoted by gold. Finally, the nucleophilic
attack by the azidosilane and allylsilane to afford the desired
pyrrolidines 2 and 3, respectively. Similarly, when heterocycles
serve as nucleophiles, the reaction undergoes subsequent Friedel-
Crafts-type alkylation to deliver the target products 4. Notably, the
observed cis stereochemistry may be the result of thermodynamic
control. This speculation is also supported by the fact that X-ray
structure of 2j is consistent with the cis product being sterically less
congested than the alternative trans product, which is consistent
with our previous results.7
R
TMS
(2 equiv)
R
1
3
PG
N
Ts
N
Ts
N
( )
6
b
3a
(1) , PG = Ts, 92%, 2:1
3c,
3d,
89%, 2:1
(3)
80%, 3:1
(4)
3b
(2) , PG = MBS, 80%, 2:1
Ts
Ts
Ts
N
MeO
N
N
Ph
3e
3f
(6) , 85%, 4:1
3g
(5) , 85%, 3:1
(7) , 93%, 4:1
Ts
N
Ts
Ts
N
F
Cl
Br
PG
N
N
N
N
PG
N
H2O
R
N
R
N3
TMS
3h
3i
3j
(8) , 82%, 5:1
(9) , 84%, 4:1
(10) , 94%, 4:1
[Au]
TMSOH + [Au]
2
D
Br
TMSN3
Ts
Ts
Ts
N
PG
N
N
( )
PG
N
PG
N
PG
6
NH
HN
[Au]
R
[Au]
R
R
R
R
3k
(11) , 73%, 4:1
3l
(12) , 85%, 4:1
3a'
(13) , 90%, 2:1
[Au]
[Au]
H2O
1
A
B
C
[Au]
a Reactions run in vials; [1] = 0.1 M; isolated yields are reported. 99% ee,
determined by HPLC on a chiral stationary phase.
b
TMS
PG
N
PG
N
Moreover, other heterocycles were also suitable carbon
nucleophiles for such a cascade cyclization, delivering the desired
heterocycle-substituted pyrrolidines 4 (Table 4). The reaction of
homopropargyl sulfonamide 1a with 5 equiv of indoles in the
presence of 5 mol % of Ph3PAuNTf2 instead of IPrAuNTf2 as
catalyst17 afforded the corresponding 2,5- disubstituted pyrrolidines
4a–4e in good yields with excellent diastereoselectivities (d.r. >
20:1). Of note, even unprotected indoles were suitable substrates
for this tandem reaction when bearing electron-withdrawing groups
on the indolel ring (Table 4, entries 3–5). Interestingly, this gold
R
TMS
TMSOH
+
[Au]
3
E
[Au]
Scheme 2 Plausible reaction mechanism.
In summary, we have developed a series of gold-catalysed
intramolecular anti-Markovnikov hydroamination-initiated
azidation, allylation and indolation reactions of chiral
homopropargyl sulfonamides. These tandem reactions enable the
rapid construction of highly functionalized pyrrolidines bearing
azido, allyl and indole moiety at the 2-position. Importantly,
complete chirality transfer is achieved in these cases. The use of
readily available substrates, a simple procedure, and mild reaction
conditions (in particular, no requirement to exclude moisture or air)
render this method potentially useful in organic synthesis.19
catalysis was also extended to the furan as
nucleophile, and the desired 2-furan-substituted pyrrolidine 4f was
obtained in 58% yield with excellent diastereoselectivity.
a heterocycle
Table 4 Reaction of chiral 1a with heterocycle nucleophiles a
Ts
We are grateful for financial support from the National Natural
Science Foundation of China (21622204 and 21772161), the Natural
Science Foundation of Fujian Province of China (2019J02001),
Ts
N
HN
( )6
Ph3PAuNTf2 (5 mol %)
DCE, 60 °C, 2 h
( )
X
X
6
1a
(5 equiv)
4
(d.r. > 20:1)
F
NFFTBS (No. J1310024), PCSIRT, and Science
Cooperation Program of Xiamen (3502Z20183015).
& Technology
Ts
N
Ts
Ts
N
( )
Conflicts of interest
There are no conflicts to declare.
N
N
6
( )
( )
Ac
N
NH
6
6
Ac
4a
4b
(2) , 71%
4c
(1) , 71%
(3) , 61%
NC
CO2Me
Notes and references
Ts
Ts
N
Ts
N
1
(a) H. Chen, M. Ni, X. Bao, C. Wang, L. Liu, W. X. Chang and J. Li, Eur.
( )
6
O
N
J. Org. Chem., 2018, 470; (b) Y. N. Bubnov, Y. Y. Spiridonov and N. Y.
Kuznetsov, Russ. Chem. Bull., 2018, 67, 345; (c) C. Y. Yu, J. K. Su, Y.
M. Jia, Y. X. Li and P. X. Rui, Faming Zhuanli Shenqing, CN
101693708A, 2010; (d) V. Liautard, V. Desvergnes, K. Itoh, H.-W. Liu
and O. R. Martin, J. Org. Chem., 2008, 73, 3103; (e) N. Chandan and
M. G. Moloney, Org. Biomol. Chem., 2008, 6, 3664.
( )
( )
NH
NH
6
6
4d
(4) , 68%
4e
(5) , 60%
4f
(6) , 58%
a Reactions run in vials; [1a] = 0.1 M; isolated yields are reported.
Based on our previous results7 and experimental observations, a
plausible mechanism to rationalize the formation of 2,5-
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2
For recent selected examples on the synthesis of 2,5-disubstituted
pyrrolidines, see: (a) D. A. Iovan, M. J. Wilding, Y. Baek, E. T.
Hennessy and T. A. Betley, Angew. Chem., Int. Ed., 2017, 56, 15599;
Shu, Y.-F. Pan, X. Lu and L.-W. Ye, Angew. Chem., IntV.ieEwd.A,r2tic0le15O,n5lin4e,
8245; (h) A.-H. Zhou, Q. He, C. Shu, Y.-F. Yu, S. Liu, T. Zhao, W. Zhang,
DOI: 10.1039/C9CC05295J
X. Lu and L.-W. Ye, Chem. Sci., 2015, 6, 1265.
(b) S. Tong, C. Piemontesi, Q. Wang, M. X. Wang and J. Zhu, Angew. 10 (a) C. Chen, S. Jin, Z. Zhang, B. Wei, H. Wang, K. Zhang, H. Lv, X.-Q.
Chem., Int. Ed., 2017, 56, 7958; (c) S. Mahato and C. K. Jana, Org.
Biomol. Chem., 2017, 15, 1655; (d) X. Wu, D. Zhang, S. Zhou, F. Gao
and H. Liu, Chem. Commun., 2015, 51, 12571; (e) Y.-F. Cheng, H.-J.
Rong, C. B. Yi, J.-J. Yao and J. Qu, Org. Lett., 2015, 17, 4758; (f) J. M.
Pierson, E. L. Ingalls, R. D. Vo and F. E. Michael, Angew. Chem., Int.
Ed., 2013, 52, 13311; (g) J. E. Redford, R. I. McDonald, M. L. Rigsby, J.
D. Wiensch and S. S. Stahl, Org. Lett., 2012, 14, 1242; (h) G. S. Lemen
and J. P. Wolfe, Org. Lett., 2010, 12, 2322.
Dong and X. Zhang, J. Am. Chem. Soc., 2016, 138, 9017; (b) J. Liu, J.
Chan, C. M. Bryant, P. A. Duspara, E. E. Lee, D. Powell, H. Yang, Z. P.
Liu, C. Walpole, E. Roberts and R. A. Batey, Tetrahedron Lett., 2012,
53, 2971; (c) A. Mordini, M. Valacchi, F. Epiroti, G. Reginato, S. Cicchi
and A. Goti, Synlett, 2011, 235; (d) S. Suga, T. Nishida, D. Yamada, A.
Nagaki and J.-I. Yoshida, J. Am. Chem. Soc., 2004, 126, 14338; (e) S. J.
Macdonald, J. E. Spooner and M. D. Dowle, Synlett, 1998, 1375; (f) L.
E. Burgess, E. K. Gross and J. Jurka, Tetrahedron Lett., 1996, 37, 3255.
3
For examples on the synthesis of chiral 2,5-disubstituted 11 For selected reviews on the Cu-catalysed azide–alkyne cycloaddition
pyrrolidines, see: (a) T. J. Osberger, D. C. Rogness, J. T. Kohrt, A. F.
Stepan and M. C. White, Nature, 2016, 537, 214; (b) M. Bergeron-
Brlek, M. Meanwell and R. Britton, Nat. Commun., 2015, 6, 6903; (c)
D. S. Daniels, A. S. Jones, A. L. Thompson, R. S. Paton and E. A.
Anderson, Angew. Chem., Int. Ed., 2014, 53, 1915; (d) I. P. Andrews
and O. Kwon, Chem. Sci., 2012, 3, 2510; (e) B. Dhudshia, B. F.
Cooper, C. L. Macdonald and A. N. Thadani, Chem. Commun., 2009,
463; (f) V. K. Aggarwal, C. J. Astle and M. Rogers-Evans, Org. Lett.,
2004, 6, 1469.
(CuAAC), see: (a) W. D. G. Brittain, B. R. Buckley and J. S. Fossey, ACS
Catal., 2016, 6, 3629; (b) J. E. Hein and V. V. Fokin, Chem. Soc. Rev.,
2010, 39, 1302; (c) M. Meldal and C. W. Tornøe, Chem. Rev., 2008,
108, 2952; for recent selected examples on the transition-metal-
catalysed reaction of TMSN3 with terminal alkynes, see: (d) Y. Ning,
Q. Ji, P. Liao, E. A. Anderson and X. Bi, Angew. Chem., Int. Ed., 2017,
56, 13805; (e) Z. Liu, P. Liao and X. Bi, Org. Lett., 2014, 16, 3668; (f)
M. Gaydou and A. M. Echavarren, Angew. Chem., Int. Ed., 2013, 52,
13468; (g) C. Qin, P. Feng, Y. Ou, T. Shen, T. Wang and N. Jiao,
Angew. Chem., Int. Ed., 2013, 52, 7850.
4
5
For recent selected reviews, see: (a) L. Huang, M. Arndt, K. Gooben,
H. Heydt and L.-J. Gooben, Chem. Rev., 2015, 115, 2596; (b) X. Zeng, 12 For selected examples on the catalytic reaction of allylsilane with
Chem. Rev., 2013, 113, 6864; (c) T.-E. Muller, K.-C. Hultzsch, M. Yus,
F. Foubelo and M. Tada, Chem. Rev., 2008, 108, 3795; (d) R. Severin
and S. Doye, Chem. Soc. Rev., 2007, 36, 1407.
terminal alkynes, see: (a) K. Motokura, S. Matsunaga, A. Miyaji, T.
Yashima and T. Baba, Tetrahedron Lett., 2011, 52, 6687; (b) E.
Yoshikawa, V. Gevorgyan, N. Asao and Y. Yamamoto, J. Am. Chem.
Soc., 1997, 119, 6781; (c) N. Asao, E. Yoshikawa and Y. Yamamoto, J.
Org. Chem., 1996, 61, 4874.
For recent selected examples, see: K. Yamamoto, Y. Yoshikawa, M.
Ohue, S. Inuki, H. Ohno and S. Oishi, Org. Lett., 2019, 21, 373; (b) M.
Liang, S. Zhang, J. Jia, C.-H. Tung, J. Wang and Z. Xu, Org. Lett., 2017, 13 For selected examples on the Au-catalysed intramolecular
19, 2526; (c) S. Zhang, B. Cheng, S. Wang, L. Zhou, C.-H. Tung, J.
Wang and Z. Xu, Org. Lett., 2017, 19, 1072; (d) J. Li, L. Lin, B. Hu, X.
Lian, G. Wang, X. Liu and X. Feng, Angew. Chem., Int. Ed., 2016, 55,
6075; (e) B. Wang, M. Liang, J. Tang, Y. Deng, J. Zhao, H. Sun, C.-H.
Tung, J. Jia and Z. Xu, Org. Lett., 2016, 18, 4614; (f) S. Zhang, Z. Xu, J.
Jia, C. H. Tung and Z. Xu, Chem. Commun., 2014, 50, 12084; (g) X.
Wang, Z. Yao, S. Dong, F. Wei, H. Wang and Z. Xu, Org. Lett., 2013,
15, 2234. (h) J. Han, B. Xu and G. B. Hammond, J. Am. Chem. Soc.,
2010, 132, 916; (i) X.-Y. Liu and C.-M. Che, Angew. Chem., Int. Ed.,
2009, 48, 2367
hydroarylation of alkynes, see:, see: (a) L. Zhang, Y. Wang, Z.-J. Yao,
S. Wang, Z.-X. Yu, J. Am. Chem. Soc., 2015, 137, 13290; (b) D.
Pflästerer, S. Schumacher, M. Rudolph, A. S. K. Hashmi, Chem.-Eur.
J., 2015, 21, 11585; (c) D. Pfl.sterer, E. Rettenmeier, S. Schneider, E.
de Las Heras Ruiz, M. Rudolph, A. S. K. Hashmi, Chem.-Eur. J., 2014,
20, 6752; (d) Z. Dong, C.-H. Liu, Y. Wang, M. Lin, Z.-X. Yu, Angew.
Chem., Int. Ed., 2013, 52, 14157; (e) L. Huang, H.-B. Yang, D.-H.
Zhang, Z. Zhang, X.-Y. Tang, Q. Xu, M. Shi, Angew. Chem., Int. Ed.,
2013, 52, 6767; (f) A. S. K. Hashmi, M. Hamzic, F. Rominger and J. W.
Bats, Chem.-Eur. J., 2009, 15, 13318; (g) A. S. K. Hashmi, M. C. Blanco,
E. Kurpejovic, W. Frey and J. W. Bats, Adv. Synth. Catal., 2006, 348,
709.
6
7
C. Shu, L. Li, T.-D. Tan, D.-Q. Yuan and L.-W. Ye, Sci. Bull., 2017, 62,
352.
For Au-catalysed cascade cyclization reactions based on 14 For recent examples on the synthesis of 2-azido-substituted
homopropargyl sulfonamides or alcohols by our group, see: (a) C.
Shu, M.-Q. Liu, Y.-Z. Sun and L.-W. Ye, Org. Lett., 2012, 14, 4958; (b)
C. Shu, M.-Q. Liu, S.-S. Wang, L. Li and L.-W. Ye, J. Org. Chem., 2013,
78, 3292; (c) Y.-F. Yu, C. Shu, C.-H. Shen, T.-Y. Li and L.-W. Ye, Chem.-
Asian J., 2013, 8, 2920; (d) Y.-F. Yu, C. Shu, B. Zhou, J.-Q. Li, J.-M.
pyrrolidines, see: (a) D. C. Marcote, R. Street-Jeakings, E. Dauncey, J.
J. Douglas, A. Ruffoni and D. Leonori, Org. Biomol. Chem., 2019, 17,
1839; (b) S. Kamijo, M. Watanabe, K. Kamijo, K. Tao and T. Murafuji,
Synthesis, 2016, 48, 115; (c) E. Nyfeler and P. Renaud, Org. Lett.,
2008, 10, 985.
Zhou and L.-W. Ye, Chem. Commun., 2015, 51, 2126; (e) C. Shu, L. Li, 15 For recent examples on the synthesis of 2-allyl-substituted
C.-H. Shen, P.-P. Ruan, C.-Y. Liu and L.-W. Ye, Chem.-Eur. J., 2016, 22,
2282; (f) Y.-F. Yu, C. Shu, T.-D. Tan, L. Li, S. Rafique and L.-W. Ye, Org.
Lett., 2016, 18, 5178; (g) C. Shu, L. Li, Y.-F. Yu, S. Jiang and L.-W. Ye,
Chem. Commun., 2014, 50, 2522; (h) Z.-S. Wang, T.-D. Tan, C.-M.
Wang, D.-Q. Yuan, T. Zhang, P. Zhu, C. Zhu, J.-M. Zhou and L.-W. Ye,
Chem. Commun., 2017, 53, 6848.
T.-D. Tan, X.-Q. Zhu, H.-Z. Bu, G.-C. Deng, Y.-B. Chen, R.-S. Liu and L.-
W.Ye, Angew. Chem., Int. Ed., 2019, 58, 9632.
For catalytic cascade cyclization reactions based on ynamides by our
group, see: (a) L. Li, X.-Q. Zhu, Y.-Q. Zhang, H.-Z. Bu, P. Yuan, J. Chen,
pyrrolidines, see: (a) M. Saito, N. Tsuji, Y. Kobayashi and Y.
Takemoto, Org. Lett., 2015, 17, 3000; (b) J. M. Pierson, E. L. Ingalls,
R. D. Vo and F. E. Michael, Angew. Chem., Int. Ed., 2013, 52, 13311;
(c) H. Yamamoto, I. Sasaki, S. Shiomi, N. Yamasaki and H. Imagawa,
Org. Lett., 2012, 14, 2266.
16 For recent examples on the synthesis of indole-substituted
pyrrolidines, see: (a) L.-H. Xie, J. Cheng, Z.-W. Luo and G. Lu,
Tetrahedron Lett., 2018, 59, 457; (b) R. Ali, G. Singh, S. Singh, R. S.
Ampapathi and W. Haq, Org. Lett., 2016, 18, 2848; (c) X. Wu, D.
Zhang, S. Zhou, F. Gao and H. Liu, Chem. Commun., 2015, 51, 12571.
8
9
J. Su, X. Deng and L.-W. Ye, Chem. Sci., 2019, 10, 3123; (b) W.-B. 17 For details, please see the Supporting Information (SI).
Shen, Q. Sun, L. Li, X. Liu, B. Zhou, J.-Z. Yan, X. Lu and L.-W. Ye, Nat. 18 CCDC 1937618 (2j)†.
Commun., 2017, 8, 1748; (c) B. Zhou, L. Li, X.-Q. Zhu, J.-Z. Yan, Y.-L. 19 For recent examples, see: (a) A. Aliyenne, F. Pin, V. D. Nimbarte, A.
Guo and L.-W. Ye, Angew. Chem., Int. Ed., 2017, 56, 4015; (d) W.-B.
Shen, X.-Y. Xiao, Q. Sun, B. Zhou, X.-Q. Zhu, J.-Z. Yan, X. Lu and L.-W.
Ye, Angew. Chem., Int. Ed., 2017, 56, 605; (e) L. Li, X.-M. Chen, Z.-S.
Wang, B. Zhou, X. Liu, X. Lu and L.-W. Ye, ACS Catal., 2017, 7, 4004;
(f) C. Shu, Y.-H. Wang, B. Zhou, X.-L. Li, Y.-F. Ping, X. Lu and L.-W. Ye,
J. Am. Chem. Soc., 2015, 137, 9567; (g) L. Li, B. Zhou, Y.-H. Wang, C.
M. Lawson, S. Comesse, M. Sanselme, V. Tognetti, L. Joubert and A.
Daïch, Eur. J. Org. Chem., 2016, 3592; (b) M. Marhold, C. Stillig, R.
Fröhlich and G. Haufe, Eur. J. Org. Chem., 2014, 5777; (c) I. Coldham
and D. Leonori, J. Org. Chem., 2010, 75, 4069; (d) P. G. Kirira, M.
Kuriyama and O. Onomura, Chem.-Eur. J., 2010, 16, 3970; (e) C.
Quinet, A. Ates and I. E. Markó, Tetrahedron Lett., 2008, 49, 5032.
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