A photoinduced Wolff rearrangement/Pd-catalyzed [3+2] cycloaddition sequence: An unexpected route to tetrahydrofurans

Article abstract of DOI:10.1039/c8cc10157d

A novel sequential reaction that combines a visible light-induced Wolff rearrangement of α-diazoketones and a Pd-catalyzed [3+2] cycloaddition of vinyl cyclopropanes with the resulting ketenes is described in this work. Selective O-allylic alkylation was observed over C-allylic alkylation, which unexpectedly led to a series of highly functionalized tetrahydrofurans with high efficiency (20 examples, 58-99% yields).

Full text of DOI:10.1039/c8cc10157d

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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc3N@C2n (2n 68 and 80). Synthesis of the
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DOI: 10.1039/C8CC10157D
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Photoinduced Wolff rearrangement/Pd-catalyzed [3+2] cyclo-
addition sequence: an unexpected route to tetrahydrofurans
Jie Liu,a Miao-Miao Li,a Bao-Le Qu,a Liang-Qiu Lu*,a,b and Wen-Jing Xiaoa,c
3Received 00th April 20xx,
Accepted 00th May 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Louie disclosed a Ni-catalyzed cycloaddition of ketenes with diynes,
affording 2,4-cyclohexadienones in moderate to good yields.6d Very
recently, by means of sequential visible light photoactivation and
asymmetric palladium catalysis, we successfully achieved [4+2]8a
and [5+2] cycloadditions8b of photogenerated ketenes (from α-
diazoketones)9,10 with Pd-containing dipoles (in-situ generated from
vinyl carbonates) (Scheme 1b).11,12 Despite these successes, it is still
desirable to use transition metal catalysis to exploit the reactivity of
ketenes for constructing new and diverse molecular skeletons.
A novel sequential reaction that combines a visible light-induced
Wolff rearrangement of α-diazoketones and a Pd-catalyzed [3+2]
cycloaddition of vinyl cyclopropanes with the resulting ketenes is
described in this work. Selective O-allylic alkylation was observed
over C-allylic alkylation, which unexpectedly led to a series of
highly functionalized tetrahydrofurans with high efficiency (20
examples, 58-99% yields).
Due to the pioneering work of Staudinger (namely, the
Staudinger ketene cycloaddition),1 ketenes have been established
as effective C2-synthons for [n+2] cycloadditions.2-4 Particularly in
the past few decades, the application of organocatalysis3 and Lewis
acid (LA) catalysis4 to this research field (Scheme 1a, left) has
resulted in many significant transformations towards structurally
diverse heterocycles. Although it is recognized as a powerful
strategy in modern organic synthesis,5 transition metal (TM)
catalysis has received less attention from the synthetic community
in the field of ketene cycloadditions and other conversions (Scheme
1a, right). As indicated by many proceeding studies, this is likely due
to the TM-promoted decarbonylation of ketenes to form stable M-
CO complexes, the cycloaddition of ketenes with M=O and ketene
homodimerizations under thermal conditions, which impede the
wide application of this catalysis strategy in ketene
transformations.6 Up to now, there were only isolated examples in
this field. In 2007, Tang, Zhou and co-workers developed a Fe-
catalyzed asymmetric olefination reaction of ketenes with
diazoacetates for synthesizing chiral allenes.7 In 2011, the group of
a) Ketene cycloadditions:
O
•
R
organocatalysis
or LA catalysis
transition metal
catalysis
well developed
underdeveloped
Ar
reactive C2-synthon
b) Our previous work:
O
R
O
C=C
C=C
R
O
Ar
Ar
O
O
O
N
O
N
O
Ph
Ts
Ts
CN
Ph
cat. [Pd]
cat. [Pd]
CN
c) This work:
CN
NC
anticipated
Pd
observed
Pd
CN
NC
C=C
C=O
R
O
O
Ar
Ar
R
normal
abnormal
cyclopentanone [3+2] cycloaddition
[3+2] cycloaddition tetrahydrofuran
•
•
In-situ formation of ketene species from -diazoketones via visible light irradiation
In-situ formation of Pd-containing dipolar species from VCPs and Pd catalysts
Scheme 1 a) Previous work on catalytic cycloadditions of ketenes. b)
Our previous work on Pd-catalyzed dipolar cycloadditions of
ketenes with vinyl carbonates. c) This work: unexpected [3+2]
cycloaddition of ketenes and VCPs.
aCCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide &
Chemical Biology, Ministry of Education, College of Chemistry, Central
China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, China.
Email: luliangqiu@mail.ccnu.edu.cn
bState Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou
Institute of Chemical Physics (LICP), Chinese Academy of Sciences,
Lanzhou 730000, China
Given that ketenes are highly electron-deficient species that can
react with carbon anions,8c we wondered whether [3+2]
cycloadditions of vinyl cyclopropanes (VCPs)13 and α-diazo ketones
could occur by means of the strategy that combines visible light
photoactivation and palladium catalysis.14 To our surprise, the
anticipated cyclopentanone via the normal [3+2] cycloadditions was
not observed (Scheme 1c, left). Instead, an unexpected
tetrahydrofurans via an abnormal [3+2] reaction was afforded with
good efficiency and selectivity (Scheme 1c, right). Notably, the
synthesis of tetrahydrofurans and their derivatives is an important
cState Key Laboratory of Organometallic Chemistry, Shanghai Institute of
Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032,
China
†Electronic supplementary information (ESI) available. See DOI:
This journal is © The Royal Society of Chemistry 20xx
Chem. Commun., 2016, 00, 1-3 | 1
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task for synthetic chemists due to their popularity in many natural prepared palladium catalyst. Delightedly, the reaction did indeed
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products and pharmaceutical and agrochemical agents.15 To this occur and the tetrahydrofuran 4aa was produced in 41% yield with
DOI: 10.1039/C8CC10157D
end, Lewis acid-catalyzed [3+2] cycloadditions of donor-acceptor the new procedure (Table 1, entry 2). Encouraged by this promising
cyclopropanes with aldehydes16 and Rh- or Cu-catalyzed [3+2] result, we evaluated a series of ligands as shown in entries 2-6 of
cycloadditions of carbonyl yildes with alkenes17 have been well Table 1. As a result, hybrid P,S-ligand L5 stood out as the optimal
established. Herein, we describe our experimental results of a novel ligand for this sequential reaction, affording the desired product in
reaction sequence by combining
a
photoinduced Wolff 63% yield (Table 1, entry 6). Routine screening of solvents (Table 1,
rearrangement and a Pd-catalyzed [3+2] cycloaddition, providing entries 6-10) indicated that DCE resulted in the best reaction
functionalized tetrahydrofuran products in good efficiency and efficiency (Table 1, entry 10: 96% yield). Control experiments
selectivity.
further indicated that both the irradiation of α-diazoketone 1a with
Initially, we performed the sequential photoinduced Wolff 6 W blue LEDs, a stepwise operation and the hybrid P,S ligand L4
rearrangement/Pd-catalyzed [3+2] cycloaddition reaction with α- were important for this sequential reaction (Table 1, entry 10 vs
diazoketone 1a and VCP 3a as the model substrates and a mixture entries 11 and 12).
of Pd2(dba)3•CHCl3 and racemic BINAP as the catalyst. Irradiation of
the reaction mixture with 6 W blue LEDs at room temperature only
produce trace amount of product 4aa. Within 10 minutes, only the
rapid decomposition of VCP 3a and slow conversion of α-
diazoketone 1a were observed (Table 1, entry 1). Then, a revised
procedure was chosen in which α-diazoketone 1a was irradiated
first for 4 h in toluene and then, the resulting ketene solution
together with VCP 3a were introduced to the solution of the pre-
After establishing the optimal conditions, we began to
determine the generality of this sequential photoinduced
Wolff rearrangement/Pd-catalyzed [3+2] cycloaddition
reaction. First, we studied the scope of α-diazoketones 1. We
generally observed excellent reaction efficiency and selectivity.
As highlighted in Table 2, aryl-substituted 1-diazopropan-2-
ones were successfully used in this sequential transformation,
regardless of the electronic feature and substitution pattern
Table 2 The generality of the sequential reactionsa,b
Table 1 Optimization of conditions for the sequential reactiona
EWG
R'
Pd2(dba)3•CHCl3
(2.5 mol%)
O
EWG
CN
CN
O
Pd2(dba)3•CHCl3
(2.5 mol%)
O
NC
•
R
O
Ar
CN
CN
NC
R
•
Me
R
Ph
L5
1.0 eq. of
(2.5 mol%)
3a
Me
Me
O
Ar
L
(2.5 mol%)
N2
O
0.2 M in DCE
rt, 4 h
Ph
Ar
N2
3a
1.0 eq. of
R'
rt, 20 min
0.2 M in solvent
rt, 4 h
Ph
1
2
4
3
rt, 20 min
1a
2a
4aa
3a
CN
O
CN
CN
O
yield (%)b
4aa
4ab
4ac
4ad
4ae
(R'' = H): 96% yield
(R'' = Me): 99% yield
(R'' = F): 98% yield
(R'' = Cl): 93% yield
(R'' = Br): 96% yield
entry
ligand
time
solvent
NC
NC
NC
Me
R''
Me
Me
1c
2
L1
L1
L2
L3
L4
L5
L5
L5
L5
L5
L5
-
10 min
9 h
toluene
toluene
toluene
toluene
toluene
toluene
DCM
trace
41
O
F
Cl
4af:
4ag:
93% yield
CN
95% yield
3
9 h
0
CN
O
CN
4
9 h
trace
33
NC
NC
Me
NC
CN
O
Me
Me
5
9 h
NC
O
O
Et
Cl
6
9 h
63
Ph
MeO
7
9 h
86
c
4ah:
4ai
4aj
4ak
98% yield
CN
: 91% yield
CN
: 98% yield
: 95% yield
CN
8
9 h
CH3CN
PhCl
56
CN
9
9 h
93
NC
NC
NC
NC
n-Bu
i-Bu
Bn
Ph
O
O
O
O
10
11c
12d
4 h
DCE
96
Ph
Ph
4am
Ph
4an
Ph
c
c
c
4al
4ao
: 61% yield
: 58% yield
: 61% yield
: 98% yield
4 h
DCE
trace
CN
CN
CN
4 h
DCE
0
NC
NC
NC
aConditions: 1a (0.4 mmol) in 2 mL of solvent was irradiated at rt
under 6 W blue LEDs for 4h; then, the resulting solution 2a together
with 3a (0.2 mmol) were added to the pre-prepared solution of
palladium complex (2.5 mol%) and ligand (5 mol%) in 2 mL of solvent
and stirred at rt for 20 minutes. bIsolated yield. cSimultaneously, add
1a and 3a to the reaction system. dNo ligand. DCM:
dichloromethane; PhCl: chlorobenzene; DCE: 1,2-dichloroethane.
BnO
O
O
O
Ph
Ph
Ph
c
c
c
4aq
4ar
4ap
: 68% yield
: 65% yield
: 94% yield
CN
CO2Et
NC
NC
Me
Me
O
O
Ph
4ba
n-Bu
Ph
X-ray
4ae
4ca
: 92% yield
: 68% yield (1.25:1 dr)
structure of
aUnless noted otherwise, reactions were implemented under the
conditions as described in entry 10 of Table 1 at 0.2 mmol scale.
O
PPh2
Ph2P
N
N
L4
O
O
PPh2
PPh2
PPh2
PPh2
PhO
P
PhO
c
bIsolated yield. The Wolff rearrangement was performed at -10 oC
N
S Ar
Bn
O
for 8 h.
(Ar = p-Br-C6H4)
L1
L2
L3
L5
2 | J. Name., 2015, 00, 1-3
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on the benzene ring. A range of tetrahydrofurans were intramolecular allylic alkylation (AA) of the O-nucleophile produces
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obtained in high reaction yields(Table 2, 4aa-4aj, 91-99% the unexpected tetrahydrofuran compoundD4OaaI: 1(B0.→10349a/aC)8, CreCp1l0a1c5i7nDg
yields). The structure of product 4ae was further confirmed the anticipated cyclopentanone 5aa via the AA process of the C-
through single-crystal X-ray diffraction analysis.18 In addition, nucleophile (B’→5aa). According to our experimental observations,
replacement of the methyl group of α-diazoketone 1a with the stepwise procedure is a good choice to ensure that enough
other linear or branched alkyl group, and benzyl or phenyl ketene molecules are present to react with intermediate A, thus
groups were also shown to be feasible, producing the reducing the decomposition of VCP 3a in the presence of palladium
corresponding products in moderate to high yields (Table 2, catalysts.
4ak-4ao, 58-98% yields). Notably, reactions with α-
O
O
•
Me
Ph
diazoketones having functional groups such as BnO, alkenyl
and alkynyl also proceeded well, likely benefiting from the mild
reaction conditions of the in situ ketene formation (Table 2,
4ap-4ar, 65-94% yields). Notably, the success of the
photoinduced Wolff rearrangement/Pd-catalyzed [3+2]
cycloaddition sequence can be further extended to other VCPs.
For example, when (E)-2-(hex-1-en-1-yl)cyclopropane-1,1-
dicarbonitrile 3b or ethyl 1-cyano-2-vinylcyclopropane-1-
carboxylate 3c was subjected to the standard reaction
conditions, the desired products 4ba and 4ca were delivered in
satisfactory yields (Table 2, 4ba, 92% yield; 4ca, 68% yield).19
Monoaryl- and dialkyl-substituted α-diazoketones were also
tested in this transformation; however, only the generation of
the ketene species and decomposition of VCPs were observed,
without the production of tetrahydrofuran products.
Me
Key points:
Ph
2a
N2
Wolff
rearrangement
1) O-AA over C-AA
2) stepwise operation
3) reactivity matching
1a
competitive VCPs
decomposition
[nucleophilic
addition]
CN
CN
Ph
CN
CN
Pd-catalyzed [3+2]
cycloaddition:
tandem C-C/C-O
bond formation
CN
O
[Pd(II)]
B
[Pd(II)]
Ph
B'
CN
O
[Pd(II)]
Me
Me
A
[oxidative addition] [intramolecular AA]
CN
CN
NC
O
NC
CN
CN
Me
[Pd(0)]
O
Ph
Ph Me
3a
4aa
5aa
Scheme 2 Proposed mechanism.
After determining the scope of this sequential reaction, we
turned our attention to probing an asymmetric variant. As
highlighted in Eq.1, when the hybrid P,S ligand L5 was replaced
with a chiral ligand L6, which was developed by our group and
exhibited high levels of enantio-control in Pd-catalyzed
decarboxylative [4+2] cycloadditions, an obvious enantio-
induction and good reaction efficiency were observed for this
reaction sequence (chiral 4aa: 91% yield and 75:25 er). In
contrast, many other classic chiral ligands, such as MonoPhos,
Trost ligand, and PHOX ligand did not result in the desired
product and R-BINAP only delivered a racemic product in 33%
yield.20
In summary, we have developed a novel photoinduced,
sequential Wolff rearrangement/Pd-catalyzed [3+2] cycloaddition
reaction of α-diazoketones and VCPs. The unexpected selectivity of
O-allylic alkylation over C-allylic alkylation in the ring-closing step
results in the formation of highly functionalized tetrahydrofurans
with high efficiency. The stepwise procedure and the choice of a
hybrid P,S ligand were two key components of this success, which
provides a direct and alternative route to generate significant
tetrahydrofuran products under mild reaction conditions.
We are grateful to the National Science Foundation of China
(No. 21822103, 21820102003, 21772052, 21772053 and
21572074), the Program of Introducing Talents of Discipline to
Universities of China (111 Program, B17019), the Natural
Science Foundation of Hubei Province (2017AHB047) and the
International Joint Research Center for Intelligent Biosensing
Technology and Health for support of this research. We also
thank Prof. Jia-Rong Chen for helpful discussion and Prof. Dr.
Fang-Fang Pan for X-ray analysis.
CN
Pd2(dba)3•CHCl3
(2.5 mol%)
O
O
NC
Me
•
Ph
Me
( 1 )
Me
L6 (2.5 mol%)
1.0 eq. of 3a
rt, 20 mins

O
Ph
N2
0.2 M in toluene
rt, 4 h
Ph
1a
2a
chiral 4aa:
91% yield, 75:25 er
Br
Ph
Ph
S
CN
PhO
PhO
CN
P
N
Bn
3a
L6
Notes and references
Next, on the basis of previously published results9,11 and our
experiences in the field of transition metal-catalyzed dipolar
cycloadditions,8,12 we proposed a possible mechanism to explain
the production of tetrahydrofuran 4 from α-diazoketone 1a and
VCP 3a. As depicted in Scheme 2, the photoinduced Wolff
rearrangement of α-diazoketone 1a first occurs under the
irradiation of blue light, producing reactive ketene species 2a which
can exist in solution at room temperature for some time. Then, the
reaction between VCP 3a and the Pd(0) catalyst generates a Pd-
containing 1,3-dipolar intermediate A. The nucleophilic addition of
the carbanion partner of A to ketene 2a generates a new
zwitterionic intermediate B and its enol tautomer B’. Finally,
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15 For selected books and reviews: (a) T. L. B. Boivin
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9
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11 For selected reviews: (a) J. D. Weaver, A. Recio. III, A. J. 17 For selected reviews: (a) A. Padwa, Acc. Chem. Res., 1991, 24,
Grenning, and J. A. Tunge, Chem. Rev., 2011, 111, 1846-1913;
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2017, 23, 13830-13857; (d) W. Guo, J. E. Gómez, À. Cristòfol, 18 CCDC 1855629 contain the supplementary crystallographic
J. Xie, A. W. Kleij, Angew. Chem. Int. Ed., 2018, 57, 13735-
13747.
data of product 4ae and it can be downloaded for free
(https://www.ccdc.cam.ac.uk).
12 Selected work from our groups: (a) L.-Q. Lu, T.-R. Li, Q. Wang 19 Please see Scheme S1 in the Supporting Information for the
and W.-J. Xiao, Chem. Soc. Rev., 2017, 46, 4135-4149; (b) Y.
unsuccessful VCPs.
Wei, L.-Q. Lu, T.-R. Li, B. Feng, Q. Wang, W.-J. Xiao and H. 20 Please see the details in the Supporting Information.
Alper, Angew. Chem. Int. Ed., 2016, 55, 2200-2204; (c) Q.
Wang, T.-R. Li, L.-Q. Lu, M.-M. Li, K. Zhang and W.-J. Xiao, J.
4 | J. Name., 2015, 00, 1-3
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DOI: 10.1039/C8CC10157D
Table of Contents Entry
Photoinduced Wolff Rearrangment
/Pd-Catalyzed [3+2] Cycloaddition Sequence
EWG2
O
O
EWG1
EWG2
EWG1
R
Ar
Pd
R
+
R'
N2
Ar
20 examples:
R'
-diazoketones
VCPs
mild reaction conditions
tetrahydrofurans
58-99% yields
•
•
•
significant products
unexpected chemoselectivity