Assessing the Activity of Lewis Bases Organocatalysts in Halonium-Induced Carbocyclization Reactions

Article abstract of DOI:10.1055/s-0036-1591982

Lewis bases were evaluated as catalysts for halocarbocyclization reactions of alkynylstyrenes and a cinnamylaniline derivative. Phosphines and phosphorus chalcogenides exhibited high activity for the conversion of alkynylstyrenes in the presence of N -halosuccinimides with up to a 30-fold increase of the initial reaction rate with respect to the background reaction. Phosphorus sulfides and selenides showed the best catalytic activity for the iodocarbocyclization of a cinnamylaniline derivative in the presence of diiodohydantoin. An asymmetric variant of the iodocarbocyclization reaction of an alkynylstyrene using a chiral phosphorus selenide resulted in a modest enantioselectivity.

Full text of DOI:10.1055/s-0036-1591982

SYNLETT
0
9
3
6
-
5
2
1
4
1
4
3
7
-
2
0
9
6
© Georg Thieme Verlag Stuttgart · New York
2018, 29, A–F
letter
A
en
C. Grandclaudon et al.
Letter
Synlett
Assessing the Activity of Lewis Bases Organocatalysts in Halonium-
Induced Carbocyclization Reactions
Charlotte Grandclaudona
Mirko Ruampsa
Raphaël Duboca
1.2 equiv
NBS
1.2 equiv
NIS
Ph
Ph
Véronique Micheleta,b
Patrick Y. Toullec*a,c
0
0
0
0
0-
0
0
2
2-
2
1
7
9-
1
1
5
CH2Cl2, rt, 2 h
CH2Cl2, rt, 2 h
Br
No catalyst: 2% yield
I
Ph
0
0
0
0
0-
0
0
3
0-
3
7
6
5-
0
5
2
No catalyst: 42% yield
with 10 mol% 5h: 80% yield
with 10 mol% 5q: 92% yield
a Institut de Recherche de Chimie Paris PSL Research University,
Chimie ParisTech-CNRS, 11 Rue P. et M. Curie, 75005 Paris,
France
b Institut de Chimie de Nice, Université Nice Sophia Antipolis
UMR CNRS, 7272 Parc Valrose, 06108 Nice, France
c Institute of Molecular Sciences University of Bordeaux, 351,
Cours de la Libération, 33405 Talence, France
patrick.toullec@u-bordeaux.fr
Se
P
P
Ph
Ph
OPh
OPh
Ph
PhO
Received: 21.02.2018
Accepted after revision: 14.03.2018
Published online: 09.04.2018
tions,4 haloaminations,5 dihalogenations,6 or the formation
of heterocycles.7 Whereas most transformations deal with
the activation of alkene functions,8 an increasing number of
reports addresses the activation of the alkyne unsatura-
tions9 towards the anti attack of a wide variety of hetero-
atomic nucleophiles, including oxygen, nitrogen, sulfur,
phosphorus, or selenium ones.
DOI: 10.1055/s-0036-1591982; Art ID: st-2018-b0883-l
Abstract Lewis bases were evaluated as catalysts for halocarbocycliza-
tion reactions of alkynylstyrenes and a cinnamylaniline derivative. Phos-
phines and phosphorus chalcogenides exhibited high activity for the
conversion of alkynylstyrenes in the presence of N-halosuccinimides
with up to a 30-fold increase of the initial reaction rate with respect to
the background reaction. Phosphorus sulfides and selenides showed
the best catalytic activity for the iodocarbocyclization of a cinnamylani-
line derivative in the presence of diiodohydantoin. An asymmetric vari-
ant of the iodocarbocyclization reaction of an alkynylstyrene using a
chiral phosphorus selenide resulted in a modest enantioselectivity.
Much less studies have been devoted to the case of the
carbon nucleophiles:10 Among these, aromatic rings sys-
tems,11 enol or enolates equivalents,12 and alkenes13 have
been efficiently involved in halocarbocyclization reactions.
As the obtainment of high yields in these reactions often re-
quires harsh conditions and/or the use of an excess of elec-
trophilic halogen agent, activation of the source of haleni-
um ions in order to increase the electrophilic power of the
halogenating agent represents a key strategy for the forma-
tion of carbon–halogen bonds under milder conditions with
respect of the green chemistry principles.14 The use of stoi-
chiometric activators involving the formation of cationic
sources of halogen atoms stabilized by Lewis bases have
been described and demonstrated both a high activity and,
in many cases, good levels of chemoselectivity in halogena-
tion reactions.11a,15,16 In the context of a challenging catalyt-
ic activation of halogenating reagents, although Lewis17 or
Brønsted18 acid catalysis as well as ion pairing catalysis19
have been reported, several contributions highlighted the
potential of Lewis base catalysis20 during the last decade as
an attractive strategy for the promotion of halofunctiona-
lization reactions of carbon unsaturations. In a seminal
contribution dealing with the bromoetherification and
bromolactonization reactions, the group of Denmark21
demonstrated the superior reactivity of different families of
Lewis bases including phosphines and phosphorus chalco-
genides such as phosphine sulfides22 and selenides, but also
sulfoxides, sulfides, disulfides, thioureas, and diselenides.
The postulated mechanism for such catalytic process relies
Key words organocatalysis, Lewis base, halogenation, carbocycliza-
tion, enynes
Long considered as chemical anomalies of nature,
organohalogen natural products have emerged as an ever-
increasing class of biologically active compounds.1 A diverse
range of organisms such as fungi, bacteria, marine plants,
marine sponges, ascidians, nudibranchs, bryozoans, corals,
insects, frogs, and even humans produce organohalogen
metabolites. The medicinal activities reported for many of
these molecules, often associated with the presence of the
halogen atoms itself,2 along with the immense structural
diversity that they exhibit, have led to an upsurge of inter-
est for methodologies enabling the creation of carbon–halo-
gen bonds.
The electrophilic activation of carbon–carbon unsatu-
rated systems by the intermediate formation of halonium
ions constitutes one of the most efficient and popular pro-
cess in synthetic organic chemistry and is involved in an
ever-increasing array of transformations due to its versatili-
ty, its cost-efficiency, its safeness, and the level of selectivi-
ty reached. This general principle is the key elemental step
for reactions such as haloesterifications,3 haloetherifica-
© Georg Thieme Verlag Stuttgart · New York — Synlett 2018, 29, A–F

B
C. Grandclaudon et al.
Letter
Synlett
on the initial nucleophilic attack of the Lewis base on the
halogen source to deliver an ionic pair of enhanced halogen
electrophilicity that will further react with carbon–carbon
unsaturations to form halonium ions (Scheme 1).
The same group25 more recently described a family of
phosphite–urea bifunctional catalysts 1 that allowed domi-
no bromo-phenoxycyclization of functionalized dienes at
diminished catalyst loadings and good levels of chemo- and
regioselectivities (Scheme 2, eq. 2). Finally, in 2017, the
group of Yamamoto26 reported the enantioselective domino
bromocarbocyclization of 1,5-polyenes using the thiophos-
phoramide 2b (Scheme 2, eq. 3). Although this report deals
with Brønsted acid catalysis, it should be stressed that the
phosphoramide 2a exhibited a low activity and no enantio-
induction, whereas the thiophosphoramide counterpart 2b
delivered the cyclized product in much higher yield and en-
antioselectivity.
A
X
X
A
X
A
+
;
LB
LB
LB
Lewis base source of electrophilic
catalyst halogen atom
ionic pair of
enhanced electrophilicity
halonium ion
Scheme 1 Mechanism of activation of halogenating reagents in the
presence of Lewis base catalysts
Taking these literature precedents into account and in
line with our interest in cyclization reactions either mediat-
ed by halogen electrophiles13f,27 or catalyzed by carbophilic
transition metals,28 we decided to engage in a study devot-
ed to the screening of Lewis base catalysts in reactions of (i)
1,5-enyne halocarbocyclization and (ii) intramolecular
haloarylation of alkenes.
As a first test experiment, we decided to investigate the
halocarbocyclization of 1-alkynyl-2-alkenylbenzene 3 in
the presence of a large set of Lewis base organocatalysts
5a–q. The cyclization of this substrate was first reported by
Sanz et al.13e,i in 2010 employing 3 equiv of N-iodosuccin-
imide (NIS) as a halogen source in refluxing CH2Cl2 for 3 h
giving the 3-iodoindene product 4 in 85% yield. Using only
Since then, several contributions have dealt with elec-
trophilic halogenations involving the use of sulfur and sele-
nium Lewis bases organocatalysts23 but their use was limit-
ed to classes of substrates involving heteroatom nucleo-
philes. Concerning the case of halocarbocyclization
reactions, the major breakthrough dates from 2007 when
Ishihara and coworkers reported the phosphine-catalyzed
cyclization of a variety of 1,5-dienes and a 1,5,9-triene
bearing a terminal electron-rich aromatic moiety acting as
a nucleophile (Scheme 2, eq. 1).24 Whereas the halogenating
agent alone fails to provide any significant conversion, addi-
tion of a phosphine promoter in catalytic amount leads to
excellent yields.
1) 1 equiv NXS
30 mol% PBu3
CH2Cl2, –78 °C, 24 h
(1)
Ph
2) ClSO3H
i-PrNO2, –78 °C, 4 h
X
H
X = Br, 81% yield
X = I, 99% yield
F3C
Ph
Ph
O
O
1) 1.1 equiv DBDMH
1.5 mol% 1
CH2Cl2, –78 °C, 24 h
Br
P
O
Br
OH
O
(2)
NH
F3C
2) CF3SO3H
i-PrNO2, –78 °C, 24 h
Br
Br
Br
O
H
HN
83% yield
d.r. 94:6
Ph
1
F3C
iPr
CF3
iPr
1) 1.05 equiv DBDMH
10 mol% 2a,b
toluene/CH2Cl2 (10:1)
iPr
X
O
–90 °C, 24 h
(3)
P
O
NHTf
iPr
2) ClSO3H
i-PrNO2, –78 °C, 4 h
Br
H
X = O 2a
X = S 2b
X = O, 20% yield e.r. 50:50
X = S, 68% yield e.r. 65:35
iPr
iPr
Scheme 2 Phosphine-, phosphite-, and thiophosphoramide-catalyzed polyene halocyclization reactions
© Georg Thieme Verlag Stuttgart · New York — Synlett 2018, 29, A–F

C
C. Grandclaudon et al.
Letter
Synlett
1.2 equiv of iodinating agent in dichloromethane at room
temperature and limiting the reaction time to 2 h, we
showed that the product was formed in 41% yield. Employ-
ing these mild conditions and fixing the catalyst loading to
10 mol%, the catalytic activity of a library of Lewis bases
was evaluated (Scheme 3). Nitrogen bases 5a,b, sulfide 5c,
selenide 5d, and disulfur 5e all displayed weak catalytic ac-
tivation of the halogenating agent, whereas the diselenide
5f led to the formation of the cyclized product in 70% yield.
mol L–1 s–1, whereas employing 5 or 10 mol% of catalyst 5q led
to initial reaction rates of 7.1·10–4 mol L–1 s–1, and 1.0·10–3
mol L–1 s–1, respectively.
10 mol% 5
1.2 equiv NIS
41% yield in the
Ph
absence of
catalyst
CH2Cl2, rt
2h
I
Ph
N
3
4
NMe2
Se
S
S
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
S
Figure 1 Reaction profile of the iodocyclization of 3 with NIS in the ab-
sence or in the presence of catalyst 5q
N
N
5a
50%
5b
36%
5c
44%
5d
58%
5e
55%
O
S
Having optimized conditions in hands (CH2Cl2, room
temperature, 1.2 equiv NIS, 10 mol% 5q), the scope of the
transformation was investigated (Scheme 4). In the case of
the enyne 6 bearing a fluoro substituent, full conversion
P
P
Se
Ph
OPh
OPh
PhO
Ph
Se
Ph
Me
Me
5f
70%
5g
69%
5h
91%
5i
90%
tBu
P
P
OR
OMe
OMe
OR
MeO
RO
R =
5j
82%
5k
89%
F
F
NIS
tBu
Se
(1)
Ph
O
P
S
P
CH2Cl2
Ph
P
Ph
Ph
Ph
Ph
Ph
Ph
6
I
Ph
Ph
Ph
7
no cat., 3 equiv NIS
40 °C, 15 h
5l
79%
5m
76%
5n
72%
79% yield (ref.13e)
10 mol% 5q
1.2 equiv NIS
rt, 2 h
O
P
S
P
Se
P
76% yield
OPh
OPh
OPh
OPh
OPh
OPh
PhO
PhO
PhO
5o
31%
5p
49%
5q
92% (87%)
Br
Br
NIS
(2)
Ph
Scheme 3 Evaluation of Lewis bases catalysts in the iodocarbocycliza-
tion of 2-alkynylstyrene 3. The yield of product 4 obtained using differ-
ent catalysts 5a-q is reported below each catalyst structure.
CH2Cl2
Ph
8
I
9
no cat., 3 equiv NIS
40 °C, 7 h
84% yield (ref.13e)
10 mol% 5q
1.2 equiv NIS
rt, 2 h
Phosphines and phosphites all gave excellent results
with yields varying from 82% for the trimethylphosphite 5j
to 91% for the triphenylphosphine 5h. The phosphorus
chalcogenides derived from triphenylphosphine all gave
good yields (72–79% for catalysts 5l–n), triphenylphospho-
roselenoate 5q led to the formation of the product in 92%
yield (87% isolated yield) whereas triphenylphosphate 5o
and triphenylphosphorothioate 5p both exhibited no sig-
nificant catalytic activities.
63% yield
5 mol% 5q
1.2 equiv NIS
OMe
(3)
CH2Cl2, rt
2 h
10
OMe
I
11
77% yield
5 mol% 5q
1.2 equiv NIS
In addition, the kinetic study of the iodocarbocycliza-
OMe
(4)
1
tion of 3 to 4 in the presence of 5q was investigated by H
CH2Cl2, rt
2 h
12
I
NMR spectroscopy using fluorene as an internal standard
(Figure 1). In the absence of catalyst, the initial reaction rate
of the transformation depicted on Scheme 3 was of 3.8·10–5
13
OMe
70% yield
Scheme 4 Scope of the 2-alkynylstyrene iodocarbocyclization in the
presence of catalyst 5q
© Georg Thieme Verlag Stuttgart · New York — Synlett 2018, 29, A–F

D
C. Grandclaudon et al.
Letter
Synlett
and a 76% isolated yield were reached after 2 h, whereas a
79% yield was reported using the original procedure13e in
the absence of catalyst, using 3 equiv of NIS at 40 °C after 15
h. In the case of the bromo-substituted substrate 8, the
noncatalyzed reaction provided the 3-iodoindene product 9
in 84% yield, when the modified version in the presence of
the Lewis base catalyst afforded 9 in 63% after 2 h (full con-
version). Using 5 mol% of 5q, alkynylstyrenes 10 and 12
were also cleanly cyclized to the iodoindenes 11 and 13 in
77% and 70% yield, respectively.
Ts
N
Ts
N
O
1.2 equiv DCDMH
5 mol% DABCO
Cl
N
N
Cl
DCE/HFIP (9:1)
0 °C, 4 h
(1)
MeO
Cl
MeO
Ph
Ph
O
15
16
DCDMH
93% yield
Ts
N
Ts
N
O
I
1.2 equiv DIDMH
N
N
I
DCE/HFIP (9:1)
0 °C, 3.5 h
(2)
I
MeO
MeO
Ph
Ph
O
In the case of the related bromocyclization of the 2-
alkynylstyrene 3, the group of Sanz reported the formation
of the bromoindene 14 in 65% yield upon reaction in the
presence of 3 equiv of N-bromosuccinimide (NBS) in reflux-
ing CH2Cl2 (Table 1, entry 1).13e Working at room tempera-
ture in the presence of 1.2 equiv NBS, only trace amounts of
product (2%, Table 1, entry 2) were detected after 2 h. Inter-
estingly, screening of the three best catalysts for the corre-
sponding iodocarbocyclization in this reaction under these
mild conditions revealed a marked boost of reactivity. The
use of 10 mol% of 5h, 5i, or 5q resulted in the formation of
the bromo derivative 14 in 82%, 73%, and 60% respectively
(Table 1, entries 3–5).
15
17
DIDMH
79% yield
Scheme 5 Intramolecular iodoarylation of cinnamylaniline 15
To evaluate the catalytic activity of Lewis base organo-
catalysts in this transformation, we decided to conduct the
tests at room temperature for 10 min. Results are reported
on Scheme 6. In the absence of catalyst, the product was
formed with a moderate 28% yield. Nitrogen Lewis bases,
such as 5a and 5b, exhibited no catalytic activity. Phos-
phines 5h and 5i and phosphine oxides 5l and 5o all had a
detrimental effect on the transformation leading to low
yields of 17 (12–25% yields). In contrast, phosphorus sele-
nides 5n and 5q led to full conversions and good yields of
the cyclization product (73% yield in both cases), whereas
phosphorus sulfide 5p exhibited the highest catalytic activ-
ity leading to the formation of 17 in 80% isolated yield.
Table 1 Lewis Base Catalyzed Bromocarbocyclization of 1,5-Enyne 3
n equiv NBS
10 mol% cat.
Ph
CH2Cl2, 2 h
Ph
Ts
N
Ts
N
temperature
Br
14
3
DIDMH 1.2 equiv
10 mol% cat.
MeO
MeO
I
Entry
Temp (°C)
NBS (equiv)
Catalysta
Yield (%)b
Ph
Ph
DCE/HFIP 9:1, rt, 10 min
15
17
1c
2
40
23
23
23
23
3
–
65
NMe2
1.2
1.2
1.2
1.2
–
2
N
3
5h
5i
5q
82 (81)
73
P
P
Ph
Ph
OPh
Ph
PhO
N
N
OPh
4
5h
25%
5i
13%
without cat.
28%
5a
25%
5b
28%
5
60
a10 mol% catalyst.
O
S
Se
P
O
P
S
P
Se
b Determined by 1H NMR spectroscopy using acetophenone as a standard,
isolated yields in brackets.
P
P
P
Ph
Ph
Ph
Ph
Ph
Ph
OPh
OPh
OPh
PhO
OPh
OPh
Ph
Ph
Ph
PhO
PhO
OPh
c Ref. 13e, reaction time not indicated.
5l
12%
5m
18%
5n
73%
5o
17%
5p
80%
5q
73%
(80%)
In a desire to evaluate Lewis bases organocatalysts in a
halocarbocyclization reaction involving the activation of an
alkene function for comparison, we focused our attention
to the tetrahydroquinoline synthesis reported by the group
of Borhan29 in 2014 and based on an intramolecular chloro-
arylation of alkenes (Scheme 5, eq. 1). We decided to inves-
tigate the corresponding iodoarylation using 1,3-diiodo-
5,5-dimethylhydantoin (DIDMH) as an electrophilic iodine
source. Remarkably, the reaction proceeded to completion
in 3.5 h at room temperature in the absence of catalyst to
give the 3-iodo-4-phenyltetrahydroquinoline 17 in 79%
yield.
Scheme 6 Evaluation of Lewis bases catalysts in the iodocarbocycliza-
tion of cinnamylaniline 15
With these results in hands, we turned our attention to
the development of an asymmetric variant of such iodo-
carbocyclization reactions featuring the use of chiral Lewis
base organocatalysts.23f,h,30 Indeed, the upsurge of interest
for the asymmetric variants of halocyclization reactions has
recently resulted in numerous studies dealing with the use
of chiral promoters,8b,31,32 but very few addressed the case
of the carbon nucleophiles.24,25c,33 Considering the pioneer-
© Georg Thieme Verlag Stuttgart · New York — Synlett 2018, 29, A–F

E
C. Grandclaudon et al.
Letter
Synlett
ing studies of Ishihara that reported the highly enantio-
selective iodocarbocyclization of polyenic substrates using
stoichiometric quantities of chiral phosphoramidite Lewis
base inducers,24 we decided to test the iodocarbocyclization
of substrates 3 and 15 in the presence of chiral phosphines
and phosphorus chalcogenides catalysts.
Supporting Information
Supporting information for this article is available online at
https://doi.org/10.1055/s-0036-1591982.
S
u
p
p
o
nrtogI
f
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S
u
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p
ortiInfogrmoaitn
References and Notes
An enantioselectivity of 14% ee was obtained using 10
mol% of the phosphoroselenoate 18 derived from a phos-
phoramidite34 in toluene at room temperature in the case of
the alkynylstyrene derivative 3 (Scheme 7) whereas only a
racemic mixture was obtained in the case of the iodo-
cyclization of substrate 15.35
(1) (a) Gribble, G. W. Acc. Chem. Res. 1998, 31, 141. (b) Gribble, G.
W. Chemosphere 2003, 52, 289. (c) Gribble, G. W. J. Chem. Educ.
2004, 81, 1441. (d) Gribble, G. W. Naturally Occurring Organo-
halogen Compounds – A: Comprehensive Update, In Progress in
the Chemistry of Organic Natural Compounds;
9
V1o.
l
Kinghorn, A. D.;
Falk, H.; Kobayashi, J., Eds.; Springer: Wien, 2010. (e) Paul, C.;
Pohnert, G. Nat. Prod. Rep. 2011, 28, 186. (f) Winterton, N. Green
Chem. 2000, 2, 173.
(2) As an example, replacement of the chlorine atoms by hydrogens
in the antibiotic vancomycin induces a decrease of the antibac-
terial activity of up to 70%, see: Harris, C. M.; Kannan, R.;
Kopecka, H.; Harris, T. M. J. Am. Chem. Soc. 1985, 107, 6652.
(3) (a) Dowle, M. D.; Davies, D. I. Chem. Soc. Rev. 1979, 8, 171.
(b) Ranganathan, S.; Muraleedharan, K. M.; Vaish, N. K.;
Jayaraman, N. Tetrahedron 2004, 60, 5273.
(4) Harding, K. E.; Tiner, T. H. In Comprehensive Organic Synthesis;
Trost, B. M., Ed.; Pergamon Press: New York, 1991, 4 363.
(5) Chemler, S. R.; Bovino, M. T. ACS Catal. 2013, 3, 1076.
(6) (a) Chambers, R. D.; James, S. R. In Comprehensive Organic
10 mol% 18
1.2 equiv NIS
*
Se
N
O
O
Ph
P
toluene, rt
2 h
4
I
Ph
3
18
14% ee
Scheme 7 Enantioselective iodocarbocyclization of 2-alkynylstyrene 3
in the presence of Lewis base catalyst 18
In this paper, we have conducted an evaluation of a vari-
ety of Lewis bases as catalysts for halocarbocyclization re-
actions involving enyne and alkenylarene substrates. The
nature of the optimal catalyst turned out to be dependent
on the nature of the class of substrates investigated and the
source of electrophilic halogen atoms used. Phosphines and
selenophosphates display high activities for the iodocarbo-
cyclization of enynes in the presence of either N-iodo or N-
bromosuccinimide, whereas phosphorus sulfides and sele-
nides exhibited the best catalytic activities for the intra-
molecular iodoarylation of alkenes in the presence of
diiodohydantoin. In the case of the iodocyclization of
enynes, up to a 30-fold increase of the initial reaction rate of
the reaction has been observed in the presence of 10 mol%
of (PhO)3PSe. Preliminary results using chiral phosphorus
selenide Lewis bases showed modest enantioselectivities (up
to 14% ee) for the iodocarbocyclization of 2-alkynylstyrenes.
Chemistry;
1
V
o.
l
Stoddart, J. F., Ed.; Pergamon Press: Oxford, 1979,
493. (b) Cresswell, A. J.; Eey, S. T. C.; Denmark, S. E. Angew. Chem.
Int. Ed. 2015, 54, 15642.
(7) For a recent review on electrophilic halogen induced heterocy-
clic synthesis, see: Godoi, B.; Schumacher, R. F.; Zeni, G. Chem.
Rev. 2011, 111, 2937.
(8) (a) Snyder, S. A.; Treitler, D. S.; Brucks, A. P. Aldrichimica Acta
2011, 44, 27. (b) Denmark, S. E.; Kuester, W. E.; Burk, M. T.
Angew. Chem. Int. Ed. 2012, 51, 10938.
(9) (a) Yamamoto, Y.; Gridnev, I. D.; Patil, N. T.; Jin, T. Chem.
Commun. 2009, 5075. (b) Hummel, S.; Kirsch, S. F. Beilstein J.
Org. Chem. 2011, 7, 847.
(10) Palisse, A.; Kirsch, S. F. Org. Biomol. Chem. 2012, 10, 8041.
(11) (a) Barluenga, J.; González, J.-M.; Campos, P. J.; Asensio, G.
Angew. Chem., Int. Ed. Engl. 1988, 27, 1546. (b) Goldfinger, M. B.;
Crawford, K. B.; Swager, T. M. J. Am. Chem. Soc. 1997, 119, 4578.
(c) Zhang, X.; Larock, R. C. J. Am. Chem. Soc. 2005, 127, 12230.
(d) Barluenga, J.; Trincado, M.; Marco-Arias, M.; Ballesteros, A.;
Rubio, E.; González, J.-M. Chem. Commun. 2005, 2008. (e) Tang,
B.-X.; Tang, D.-J. S.; Yu, Q.-F.; Zhang, Y.-H.; Liang, Y.; Zhong, P.;
Li, J.-H. Org. Lett. 2008, 10, 1063.
Funding Information
(12) (a) Cossy, J.; Thellend, A. Tetrahedron Lett. 1990, 31, 1427.
(b) Kitagawa, O.; Inoue, T.; Hirano, K.; Taguchi, T. J. Org. Chem.
1993, 58, 3106. (c) Bi, H.-P.; Guo, L.-N.; Duan, X.-H.; Gou, F.-R.;
Huang, S.-H.; Liu, X.-Y.; Liang, Y.-M. Org. Lett. 2007, 9, 397.
(d) Barluenga, J.; Palomas, D.; Rubio, E.; González, J. M. Org. Lett.
2007, 9, 2823. (e) Ali, Z.; Wirth, T. Org. Lett. 2009, 11, 229.
(13) (a) Schreiner, P. R.; Prall, M.; Lutz, V. Angew. Chem. Int. Ed. 2003,
42, 5757. (b) Matsumoto, S.; Takase, K.; Ogura, K. J. Org. Chem.
2008, 73, 1721. (c) Lim, C.; Rao, S.; Shin, S. Synlett 2010, 368.
(d) Crone, B.; Kirsch, S. F.; Umland, K.-D. Angew. Chem. Int. Ed.
2010, 49, 4661. (e) Sanz, R.; Martinez, A.; Garcia-Garcia, P.;
Fernandez-Rodriguez, M. A.; Rashid, M. A.; Rodriguez, F. Chem.
Commun. 2010, 46, 7427. (f) Pradal, A.; Nasr, A.; Toullec, P. Y.;
Michelet, V. Org. Lett. 2010, 12, 5222. (g) Harschneck, T.; Kirsch,
S. F.; Wegener, M. Synlett 2011, 1151. (h) Huber, F.; Kirsch, S. F.
This work was supported by a grant (ANR-13-JS07-0010) from the
Agence Nationale de la Recherche. This work was also supported by
the Ministère de l’Education et de la Recherche and the Centre Na-
tional de la Recherche Scientifique (CNRS).
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Acknowledgment
The authors are grateful to ANR and CNRS. Julien Gicquiaud and Mile-
na Rives are kindly acknowledged for performing additional experi-
ments.
© Georg Thieme Verlag Stuttgart · New York — Synlett 2018, 29, A–F

F
C. Grandclaudon et al.
Letter
Synlett
J. Org. Chem. 2013, 78, 2780. (i) Garcia-Garcia, P.; Sanjuán, A. M.;
Rashid, M. A.; Martinez-Cuezva, A.; Fernandez-Rodriguez, M. A.;
Rodriguez, F.; Sanz, R. J. Org. Chem. 2017, 82, 1155.
(27) Grandclaudon, C.; Michelet, V.; Toullec, P. Y. Synlett 2018, 29,
310.
(28) (a) Pradal, A.; Gladiali, S.; Michelet, V.; Toullec, P. Y. Chem. Eur. J.
2014, 20, 7128. (b) Pradal, A.; Chen, Q.; Faudot dit Bel, P.;
Toullec, P. Y.; Michelet, V. Synlett 2012, 23, 74. (c) Pradal, A.;
Chao, C.-M.; Toullec, P. Y.; Michelet, V. Beilstein J. Org. Chem.
2011, 7, 1021. (d) Pradal, A.; Chao, C.-M.; Vitale, M. R.; Toullec,
P. Y.; Michelet, V. Tetrahedron 2011, 67, 4371. (e) Toullec, P. Y.;
Blarre, T.; Michelet, V. Org. Lett. 2009, 11, 2888. (f) Chao, C.-M.;
Beltrami, D.; Toullec, P. Y.; Michelet, V. Chem. Commun. 2009,
6988. (g) Chao, C.-M.; Toullec, P. Y.; Michelet, V. Tetrahedron
Lett. 2009, 50, 3719. (h) Chao, C.-M.; Vitale, M.; Toullec, P. Y.;
Genêt, J.-P.; Michelet, V. Chem. Eur. J. 2009, 15, 1319. (i) Chao, C.-
M.; Genin, E.; Toullec, P. Y.; Genêt, J.-P.; Michelet, V. J.
Organomet. Chem. 2009, 694, 538. (j) Leseurre, L.; Chao, C.-M.;
Seki, T.; Genin, E.; Toullec, P.-Y.; Genêt, J.-P.; Michelet, V. Tetrahe-
dron 2009, 65, 1911. (k) Leseurre, L.; Toullec, P. Y.; Genêt, J.-P.;
Michelet, V. Org. Lett. 2007, 9, 4049. (l) Genin, E.; Leseurre, L.;
Toullec, P. Y.; Genet, J.-P.; Michelet, V. Synlett 2007, 1780.
(m) Toullec, P. Y.; Genin, E.; Leseurre, L.; Genêt, J.-P.; Michelet, V.
Angew. Chem. Int. Ed. 2006, 45, 7427. (n) Nevado, C.; Charruault,
L.; Michelet, V.; Nieto-Oberhuber, C.; Muñoz, M. P.; Méndez, M.;
Rager, M.-N.; Genêt, J.-P.; Echavarren, A. M. Eur. J. Org. Chem.
2003, 706.
(29) Ashtekar, K. D.; Marzijarani, N. S.; Jaganathan, A.; Holmes, D.;
Jackson, J. E.; Borhan, B. J. Am. Chem. Soc. 2014, 136, 13355.
(30) For a seminal contribution on phosphate-catalyzed enantiose-
lective halolactonisation, see: (a) Nakatsuji, H.; Sawamura, Y.;
Sakakura, A.; Ishihara, K. Angew. Chem. Int. Ed. 2014, 53, 6974.
For a seminal contribution on phosphane-catalyzed enantiose-
lective bromo-O-amidation, see: (b) Kawato, Y.; Kubota, A.;
Ono, H.; Egami, H.; Hamashima, Y. Org. Lett. 2015, 17, 1244.
(31) For reviews on asymmetric halogenation reactions, see:
(a) Cheng, Y. A.; Yu, W. Z.; Yeung, Y.-Y. Org. Biomol. Chem. 2014,
12, 2333. (b) Tan, C. K.; Yeung, Y.-Y. Chem. Commun. 2013, 49,
7985. (c) Castellanos, A.; Fletcher, S. P. Chem. Eur. J. 2011, 17,
5766. (d) Chen, G.; Ma, S. Angew. Chem. Int. Ed. 2010, 49, 8306.
(e) Ibrahim, H.; Togni, A. Chem. Commun. 2004, 1147.
(14) (a) Anastas, P. T.; Warner, J. C. Green Chemistry: Theory and
Practice; Oxford University Press: New York, 2000. (b) Anastas,
P. T.; Bartlett, L. B.; Kirchhoff, M. M.; Williamson, T. C. Catal.
Today 2000, 55, 11.
(15) (a) Neverov, A. A.; Brown, R. S. J. Org. Chem. 1998, 63, 5977.
(b) Brown, R. S.; Nagorski, R. W.; Bennet, A. J.; McClung, R. E. D.;
Aarts, G. H. M.; Klobukowski, M.; McDonalds, R.; Santarsiero, B.
D. J. Am. Chem. Soc. 1994, 116, 2448.
(16) (a) Snyder, S. A.; Treitler, D. S. Angew. Chem. Int. Ed. 2009, 48,
7899. (b) Snyder, S. A.; Treitler, D. S.; Brucks, A. P. J. Am. Chem.
Soc. 2010, 132, 14303.
(17) Kang, S. H.; Lee, S. B.; Park, C. M. J. Am. Chem. Soc. 2003, 125,
15748.
(18) Huang, D.; Wang, H.; Xue, F.; Guan, H.; Li, L.; Peng, X.; Shi, Y.
Org. Lett. 2011, 13, 6350.
(19) (a) Veitch, G. E.; Jacobsen, E. N. Angew. Chem. Int. Ed. 2010, 49,
7332. (b) Rauniyar, V.; Lackner, A. D.; Hamilton, G. L.; Toste, F. D.
Science 2011, 334, 1681.
(20) Denmark, S. E.; Beutner, G. L. Angew. Chem. Int. Ed. 2008, 47,
1560.
(21) Denmark, S. E.; Burk, M. T. Proc. Natl. Acad. Sci., U.S.A. 2010, 107,
20655.
(22) For phosphine sulfide catalyzed halogenation reactions, see:
(a) Maddox, S. M.; Nalbandian, C. J.; Gustafson, J. L. Org. Lett.
2015, 17, 1042. (b) Wong, Y.-C.; Ke, Z.; Yeung, Y.-Y. Org. Lett.
2015, 17, 4944. (c) Ke, Z.; Wong, Y.-C.; See, J. Y.; Yeung, Y.-Y. Adv.
Synth. Catal. 2016, 358, 1719.
(23) (a) Mellegaard, S. R.; Tunge, J. A. J. Org. Chem. 2004, 69, 8979.
(b) Mellegaard-Waetzig, S. R.; Wang, C.; Tunge, J. A. Tetrahedron
2006, 62, 7191. (c) Cresswell, A. J.; Eey, S. T.-C.; Denmark, S. E.
Nat. Chem. 2015, 5, 146. (d) Balkrishna, S. J.; Prasad, C. D.;
Panini, P.; Detty, M. R.; Chopra, D.; Kumar, S. J. Org. Chem. 2012,
77, 9541. (e) Tay, D. W.; Tsoi, I. T.; Er, J. C.; Leung, G. Y. C.; Yeung,
Y.-Y. Org. Lett. 2013, 15, 1310. (f) Chen, F.; Tan, C. K.; Yeung, Y.-Y.
J. Am. Chem. Soc. 2013, 135, 1232. (g) Cheng, Y. A.; Chen, T.; Tan,
C. K.; Heng, J. J.; Yeung, Y.-Y. J. Am. Chem. Soc. 2012, 134, 16492.
(h) Ke, Z.; Tan, C. K.; Chen, F.; Yeung, Y.-Y. J. Am. Chem. Soc. 2014,
136, 5627. (i) Zhou, L.; Tan, C. K.; Jiang, X.; Chen, F.; Yeung, Y.-Y. J.
Am. Chem. Soc. 2010, 132, 15474. (j) Tan, C. K.; Le, C.; Yeung, Y.-
Y. Chem. Commun. 2012, 48, 5793. (k) Chen, J.; Zhou, L.; Tan, C.
K.; Yeung, Y.-Y. J. Org. Chem. 2012, 77, 999. (l) Hernándes-Torres,
G.; Tan, B.; Barbas, C. F. III. Org. Lett. 2012, 14, 1858.
(24) Sakakura, A.; Ukai, A.; Ishihara, K. Nature 2007, 445, 900.
(25) (a) Sawamura, Y.; Nakatsuji, H.; Sakakura, A.; Ishihara, K. Chem.
Sci. 2013, 4, 4181. (b) Sawamura, Y.; Nakatsuji, H.; Akakura, M.;
Sakakura, A.; Ishihara, K. Chirality 2014, 26, 356. (c) Sawamura,
Y.; Ogura, Y.; Nakatsuji, H.; Sakakura, A.; Ishihara, K. Chem.
Commun. 2016, 52, 6068.
(32) For a related enantioselective carbosulfenylation of alkenes in
the presence of a chiral phosphorus selenide Lewis base cata-
lyst, see: (a) Denmark, S. E.; Jaunet, A. J. Am. Chem. Soc. 2013,
135, 6419. (b) Denmark, S. E.; Hartmann, E.; Kornfilt, D. J. P.;
Wang, H. Nat. Chem. 2014, 1056.
(33) Wolstenhulme, J. R.; Rosenqvist, J.; Lozano, O.; Ilupeju, J.; Wurz,
N.; Engle, K. M.; Pidgeon, G. W.; Moore, P. R.; Stanford, G.;
Gouverneur, V. Angew. Chem. Int. Ed. 2013, 52, 9796.
(34) (a) Feringa, B. L. Acc. Chem. Res. 2000, 33, 346. (b) Teichert, J. F.;
Feringa, B. L. Angew. Chem. Int. Ed. 2010, 49, 2486.
(35) See the Supporting Information for a summary of asymmetric
chiral Lewis base-catalyzed iodocyclization of substrates 3 and
15.
(26) Samanta, R. C.; Yamamoto, H. J. Am. Chem. Soc. 2017, 139, 1460.
© Georg Thieme Verlag Stuttgart · New York — Synlett 2018, 29, A–F