Iron-catalyzed acylation-functionalization of unactivated alkenes with aldehydes

Article abstract of DOI:10.1039/d0cc06774a

Herein, an iron-catalyzed acylation-functionalization of unactivated alkenes with aldehydes via distal group ipso-migration is reported. This strategy overcame the energy barrier and reversibility in the difunctionalization of unactivated alkenes with nuc

Full text of DOI:10.1039/d0cc06774a

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DOI: 10.1039/D0CC06774A
Journal Name
COMMUNICATION
Iron-Catalyzed Acylation-Functionalization of Unactivated
Alkenes with Aldehydes
Received 00th January 20xx,
Accepted 00th January 20xx
Tian Tian, Xin Wang, Leiyang Lv* and Zhiping Li*
DOI: 10.1039/x0xx00000x
www.rsc.org/
Herein, an iron-catalyzed acylation-functionalization of which cyclic C-C bond cleavage to give the functionalized
unactivated alkenes with aldehydes via distal group ipso- products.
migration was reported. This strategy overcomed the
(a) Difunctionalization of unactivated alkenes with distal function group ipso-migration strategy
energy barrier and reversibility in the difunctionalization of
OH
MG
R2
O
n = 0, 2, 3
unactivated alkenes with nucleophilic acyl radicals, and a
variety of β-(hetero)arylated, -cyanated and -oximated
unsymmetrical 1,6- and 1,7-diketones were obtained
regioselectively, chemoselectively and efficiently.
R1
( )n
+
Radicals
R
R1 ( )n
-H
MG
R2
R = CF3, CF2R, SCF3, P(O)R2,
N3, SiR3, C(O)Ar, SO2Ar, etc.
OH
R
MG
R2
OH
R1 ( )n
R1
( )n
MG
R = acyl
R
R
MG
( )n
R2
HO
R1
R
R2
Controlled radical-mediated difunctionalization of alkenes is
a state-of-the-art strategy for the utilization of alkenes.1 In the
past few decades, great progress has been made in the
manipulation of activated alkenes in which an adjacent π-
system (e.g., aryl, carbonyl and heteroatom) was installed.2 The
requirement of such activation group was attributed to (1) the
lowered LUMO energy of C=C double bond with the aid of
vicinal π-system, which facilitates its interaction with SOMO of
free radical; (2) the stabilization of incipient alkyl radical
intermediate via p-π conjugation or p-p orbital delocalization
with the heteroatom. In contrast, the analogous conversion of
unactivated alkenes (e.g., aliphatic alkenes) remains challenge
task. To overcome this conundrum, chemists have developed
the intramolecular radical functional group migration strategy
as a powerful solution to realize this goal.3 Early reports from
Tu’s group4 and Wu/Li5 group in 2013 realized the tandem
trifluoromethylation/semipinacol rearrangement of allylic
alcohols, in which a radical 1,2-aryl migration was indicated in
the case of diarylallylic substrates used. Remarkably, Zhu and
co-workers have innovatively developed the intramolecular
distal functional group ipso-migration (FGM) strategy recently,
which has well been applicable to radical difunctionalization of
unactivated alkenes (Scheme 1a).6 This protocol was proposed
to proceed through extrinsic radical addition to alkene, the
newly formed alkyl radical rapidly captured by intramolecular
1,n (n = 4, 5) unsaturated migratory group (e.g., heteroaryl,7
cyano,8 formyl,9 oximino,10 alkynyl11 and alkenyl12), upon
MG = Migration Group = heteroaryl, cyano, formyl, oximino, alkyne, alkene etc.
(b) Photocatalytic aroylation of unactivated alkenes with aromatic acid chlorides (Ngai, 2019)
OH
MG
( )n
O
O
O
R
fac-Ir(ppy)3
( )n
+
R'
Cl
Ar
100 W Blue LED
R
Ar
MG
R'
(c) Aldehydes mediated acylation-functionalization of unactivated alkenes (This work)
O
R
OH
( )n
R1
O
Fe
( )n
R
+
MG
O
H
R1
(t-BuO)2, heat
ipso-migration
MG
R and R1 = aryl, heteroaryl, alkyl
n = 1, 2
-functionalized 1,6- & 1,7-diketones
H
HetAr
MG
=
N
N
OBn
Heteroarene
Nitrile
Bn-oxime
Scheme 1. Distal functional group ipso-migration strategy and its application in the
acylation-functionalization of unactivated alkenes.
Carbonyls are important and versatile building blocks both in
synthetic and industrial communities. Long-chain diketones,
especially unsymmetrical 1,6- and 1,7-diketones, are found
broad applications in the synthesis of bioactive cyclic
molecules, while the efficient protocols to prepare these
structures are still limited.13 Recently, the synthesis of
unsymmetric 1,8-diketones was achieved efficiently by the
FGM strategy.14 Hence, it is highly desirable to develop a
general and wide-applicable strategy that enables rapid access
to these diketone skeletons. Aldehydes are cheap, easily
available and naturally-abundant feedstocks. Our group has
long been interested in the iron-catalyzed15 reactivity of acyl
radicals16 generated from aldehydes with alkenes. In our
a. Department of Chemistry, Renmin University of China, Beijing 100872 (China)
E-mail: lvleiyang2008@163.com; zhipingli@ruc.edu.cn
Electronic Supplementary Information (ESI) available: copies of 1H NMR and 13C
NMR Spectra for new compounds. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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COMMUNICATION
Journal Name
entry
1
2
catalyst
FeCl2
CuCl
oxidant
solvent View3Aartaic(l%e O)bnline
previous work,17 activated alkenes, for example, styrenes and
acrylates, could react efficiently with acyl radicals to give the
difunctionalization products due to the intrinsic nucleophilic
nature of acyl radicals. While its addition to unactivated
(electron-rich) alkenes needs to overcome higher activation
energy, and this process tends to be reversible, trapping the
generated alkyl radical intermediate with another functional
group except hydrogen atom is quite difficult.
We wonder if this limitation can be overcome with
unactivated alkenes tethered to substituted tertiary alcohols as
substrates using Zhu’s intramolecular distal group ipso-
migration strategy. Our key consideration is that intramolecular
migration group capture of newly-formed alkyl radical is faster
than itself decomposition (Scheme 1a, dashed line, R = acyl).
Notably, during the progress of our project, Ngai and co-
workers reported the use of aroyl chlorides as aroyl radical
sources for such transformations under iridium/blue LED
(Scheme 1b).18 Herein, we wish to report our results that using
aldehydes as acyl radical sources for the difunctionalization of
unactivated alkenes under iron-catalyzed thermo conditions
(Scheme 1c). Abundant aldehydes were applicable, and a
variety of β-(hetero)arylated, -cyanated and -oximated
unsymmetrical 1,6- and 1,7-diketones were obtained selectively
and efficiently.
DOI: 10.1039/D0CC06774A
(t-BuO)2
(t-BuO)2
(t-BuO)2
(t-BuO)2
(t-BuO)2
(t-BuO)2
(t-BuO)2
(t-BuO)2
(t-BuO)2
(t-BuO)2
(t-BuO)2
(t-BuO)2
(t-BuO)2
(t-BuO)2
t-BuOOH
PhCOOOtBu
(PhCOO)2
(t-BuO)2
(t-BuO)2
—
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
PhMe
MeCN
EA
69
56
3
CoCl2
PdCl2
AgNO3
FeBr2
FeI2
29
4
18
5
37
6
28
7
45
8
Fe2(CO)9
Fe(acac)2
FeCl2
FeCl2
FeCl2
FeCl2
FeCl2
FeCl2
FeCl2
FeCl2
FeCl2
—
56
9
62
10
11c
12c
13c
14
15
16
17
18d
19
20
22
48
34
DCE
DMF
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
N. D.
N. D.
20
12
31
86(80)
47
FeCl2
N. D.
aReaction conditions: 1a (0.3 mmol), 2a (1.5 mmol), catalyst (2.5 mol%),
oxidant (0.75 mmol), solvent (2.0 mL), 120 C, 3 h, under N2 unless other
noted. bNMR yields were determined by 1H NMR using an internal standard
(the isolated yield in parentheses). cSealed tube was used. d1.5 mol% of
FeCl2 used.
o
We started the investigation of 1-(benzo[d]thiazol-2-yl)-1-
phenylpent-4-en-1-ol 1a and benzaldehyde 2a as the model to
test our hypothesis (Table 1). Gratifyingly, after preliminary
screening, the desired ipso-migration difunctionalization
product 3aa was obtained in 69% yield with FeCl2 as the
catalyst and di-tert-butyl peroxide (DTBP) as oxidant in the
With the optimal reaction conditions identified, we set out to
examine the generality of this protocol. As shown in Scheme 2,
chemoselective migration of benzothiazolyl group over aryl
group was observed in spite of its electronic and steric
characteristics. For example, aromatic rings bearing electron-
donating -Me, -tBu or -OMe groups on the para-position gave
products 3ab-3ad in 71-84% yields. Arenes with electron-
withdrawing halides, especially bromide, remained untouched,
which allowed for further functionalization via cross-coupling
reactions (3ae-3ah). The yields were not influenced when
substituent attached to the meta- or ortho-position (3ai and 3aj).
The substrates containing naphthyl, thiophenyl, as well as alkyl
substituent such as cyclohexyl, were all compatible under the
optimized conditions (3ak-3am). This transformation can also
be extended to the difunctionalization of 2,2-disubstituted
alkenes, affording the product 3an in 68% yield with a
quaternary carbon center. Based on the above results, we then
examined other types of migrating groups. Hetero aromatic
rings such as benzoxazole, imidazole, thiophene and quinoline
all migrated smoothly to give the desired products 3ao-3ar in
41-65% yields. Gratifyingly, nitrile and Bn-oxime could also
migrate and afforded functionalized unsymmetrical 1,6-
diketones (3as-3at). Besides, gram-scale experiment of 1c and
2a was carried out to prove the practicability of this protocol
(3ac, 0.75g, 55%).
o
presence of chlorobenzene under 120 C for 3 h (entry 1).
Different kind of metal catalysts were then investigated and
revealed that the desired 3aa could also be obtained with CuCl,
CoCl2, PdCl2, or AgNO3, yet the yields were not as good as
FeCl2 (entries 2−5). The other iron catalysts, such as FeBr2,
FeI2, Fe2(CO)9 and Fe(acac)2, delivered 3aa in 28-62% yields
(entries 6-9). Solvent optimization revealed that toluene (PhMe),
acetonitrile (MeCN) and ethyl acetate (EA) gave inferior yields
of ipso-migration product 3aa (entries 10-12), while no 3aa
was detected in the presence of 1,2-dichloroethane (DCE) or
N,N-dimethylformamide (DMF) (entries 13 and 14). Other
oxidants, such as tert-butyl hydroperoxide (TBHP), tert-butyl
peroxybenzoate (TBPB) and benzoyl peroxide (BPO) were less
efficient in this transformation (entries 15−17). Notably, the
reaction could afford the desired product 3aa in 86% yield
when reducing the FeCl2 loading to 1.5 mol% (entry 18).
Control experiments revealed that 3aa was furnished in 47%
yield in the absence of metal catalyst (entry 19), while 3aa was
not detected without adding oxidant (entry 20).
Table 1 Optimization of the reaction conditionsa
O
Ph
O
Ph
S
H
Ph
N
O
catalyst, oxidant
solvent
O
+
N
S
Ph
1a
2a
3aa
2 | J. Name., 2012, 00, 1-3
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Journal Name
COMMUNICATION
R1 OH
O
O
FeCl2 (1.5 mol%)
(t-BuO)2 (2.5 equiv)
PhCl (2.0 mL), 120 oC, 3 h
R2
O
View Article Online
R
Ph
Ph OH
R1
Ph
FeCl2 (1.5 mol%)
(t-BuO)2 (2.5 equiv)
PhCl (2.0 mL), 120 oC, 3 h
+
MG
DOI: 10.1039/D0CCO06774A
O
R2
Ph
H
S
O
S
N
+
MG
R
H
N
1
2a
3
1a
2
3
Me
O
O
3ab
R = 4-Me,
, 71%
, 84%
O
O
O
3ac
R = 4-t-Bu,
Ph
Me
Ph
Ph
Ph
Ph
(3.0 mmol, 0.75 g, 55%)
R
O
O
Me
R
O
3ad
R = 4-OMe,
, 72%
, 74%
3af
S
N
S
N
O
R = 2-naph, 3ak, 48%
O
S
N
3ae
S
N
R = 4-F,
R = 4-Cl,
R = 4-Br,
S
N
3al
, 51%
3am
R = 2-thio,
, 70%
3ag
R = c-hex,
, 59%
, 67%
3ah
R = 4-CF3,
, 71%
3ba
3ca
3da
, 66%
, 71%
, 66%
3ai
3aj
R = 3-Me,
R = 2-Me,
, 73%
, 70%
t-Bu
Ph
OMe
O
O
O
Ph
Ph
Ph
O
O
O
O
Me
O
O
N
O
Ph
Ph
Ph
Ph
S
N
S
S
N
Ph
Ph
Ph
Ph
O
O
O
O
Me
N
N
S
S
N
O
N
3ea
3fa
3ga
, 70%
, 72%
, 61%
F
Cl
Br
3an
3ao
3ap
3aq
, 52%
, 68%
, 45%
, 41%
O
O
O
Ph
Ph
Ph
O
O
N
O
Nitrile-migration
Bn-oxime-migration
O
S
N
S
S
N
Ph
O
O
Ph
Ph
Ph
O
Ph
Ph
N
O
O
3ha
, 62%
3ia
3ja
, 63%
, 68%
MG
MG
CF3
O
S
O
O
H
N
Ph
Ph
3at
, 52%
N
3as, 41%
MG
=
Ph
3ar
MG
, 65%
=
O
OBn
O
N
O
S
N
S
S
N
Scheme 2 Scope of unactivated alkenes. Reaction conditions: 1 (0.3 mmol),
benzaldehyde 2a (1.5 mmol), FeCl2 (1.5 mol%), (t-BuO)2 (0.75 mmol), PhCl (2.0
mL), 120 oC, 3 h, under N2. Reported yields were isolated yields and based on 1.
3la
3ma
, 51%
O
, 32%
3ka
, 59%
Ph
O
Ph
O
We next examined the reaction with respect to the readily
available aldehydes (Scheme 3). Electron-rich aldehydes, such
as (o, m or p)-tolualdehyde, p-tert-butyl benzaldehyde, biphenyl
formaldehyde and anisyl aldehyde, all reacted smoothly with 1a
to deliver the desired products (3ba-3ga) in 61-72% yields.
Aldehydes with halogen functionalities attached also underwent
the ipso-migration difunctionalization to give the corresponding
1,6-diketiones (3ha-3ja) in good yields. When strong electron-
withdrawing CF3 attached on the aldehyde, the yield was
decreased to 59%. Other aromatic aldehydes such as 2-
naphthaldehyde (2l) and thiophene-2-carbaldehyde (2m) were
also applicable for this transformation (3la and 3ma). Notably,
valeraldehyde (2n) afforded the unsymmetrical 1,6-diketone
3na in 8% yield along with the decarbonylativeproduct 3na' in
29% yield. The results indicated that the decarbonylation of
aliphatic aldehyde is predominant under the present conditions.
The alkyl chain length of the alkene substrates on the ipso-
heteroaryl migration efficiency was then examined. As shown
in Table 2, 5a was obtained in 9% yield when 4a was used as
substrate. The desired products 3aa and 5c were obtained
smoothly in 80% and 57% yield, respectively, while the
corresponding 5b and 5d were not observed. These results
indicated that the formation of three-, five- or six-membered
cyclic transition state is thermodynamically favoured.
+
S
N
S
N
a
a
3na
3na'
, 8%
, 29%
Scheme 3 Scope of aldehydes. Reaction conditions: 1a (0.3 mmol), 2 (1.5 mmol),
FeCl2 (1.5 mol%), (t-BuO)2 (0.75 mmol), PhCl (2.0 mL), 120 oC, 3 h, under N2
unless other noted. Reported yield were isolated yields and based on 1a. a3.0
mmol of valeraldehyde and 1.5 mmol of (t-BuO)2 used, 12 h.
Table 2 Examination of the chain length on the reaction efficiency.
Ph OH
O
S
N
S
( )n
+
N
S
O
O
O
Ph
H
HO
Ph
N
( )n
Ph
( )n
Ph
Ph
1a, 4a-4d
2a
TS
3aa, 5a-5d
substrates
4a
4b
1a
4c
4d
, n = 0
3
, n = 1
4
, n = 2
5
, n = 3
6
, n = 4
7
TS ring size
products (%)
5a
5b
3aa
5c
5d
, 0
, 9
, 0
, 80
, 57
Based on the above results and previous reports,6-11
a
possible reaction mechanism for this ipso-migration
difunctionalization of unactivated alkenes was proposed
(Scheme 4). Initially, FeII mediated cleavage of DTBP under
heating gives t-BuO- and t-BuO•, which abstracts the aldehyde
hydrogen to deliver acyl radical A. Then addition of A to the
C=C bond in 1a produces β-carbonyl carbon radical B, which is
trapped by C=N bond to afford more stable nitrogen radical
intermediate D. Intramolecular radical ipso-migration proceeds
Control experiments showed that the reaction of 1a with 2a
was completely suppressed when the radical inhibitors 2,2,6,6-
tetramethylpipedinyloxy (TEMPO) or butylatedhydroxytoluene
(BHT) was added. Notably, the TEMPO-aldehyde adduct was
detected in GC-MS, suggesting that the existence of acyl
radical in this transformation (see Supporting Information).
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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Journal Name
Y. He, G. Li and M. Yuan, Chem. CommuVnie.,w 2Ar0tic1le7,On5lin3e,
sequentially. Finally, oxidation by FeIII and deprotonation by t-
BuO- gives the desired product 3aa.
12946-12949; (d) C. Pan, Q. Ni, Y. Fu and J.-T. Yu, J. Org.
DOI: 10.1039/D0CC06774A
Chem., 2017, 82, 7683−7688. (e) J. Fang, W.-L. Dong, G.-Q.
Xu and P.-F. Xu, Org. Lett., 2019, 21, 4480−4485; (f) D.
Chen, Z. Wu, Y. Yao and C. Zhu, Org. Chem. Front., 2018,
5, 2370-2374; (g) H. Zhang, X. Wu, Q. Zhao and C. Zhu,
Chem. Asian J., 2018, 13, 2453–2457.
t-BuOH
HO
Ph OH
O
O
1a
O
Ph
Ph
S
Ph
H
Ph
S
N
O
Ph
N
A
2a
C
B
8
9
(a) Z. Wu, R. Ren and C. Zhu, Angew. Chem., Int. Ed., 2016,
55, 10821−10824; (b) M. Ji, Z. Wu, J. Yu, X. Wan and C.
Zhu, Adv. Synth. Catal., 2017, 359, 1959–1962; (c) Y. Kwon
and Q. Wang, Org. Lett., 2020, 22, 4141–4145; (d) N. Wang,
L. Li, Z.-L. Li, N.-Y. Yang, Z. Guo, H.-X. Zhang and X.-Y.
Liu, Org. Lett., 2016, 18, 6026–6029; (e) R. Ren, Z. Wu, L.
Huan and C. Zhu, Adv Synth Catal., 2017, 359, 3052–3056.
J. Yu, D. Wang, Y. Xu, Z. Wu and C. Zhu, Adv. Synth. Catal.,
2018, 360, 744 –750.
(t-BuO)2
t-BuO
t-BuO
+
3aa
heat
ipso
-migration
t-BuOH
t-BuO
[FeII]
[FeIII
]
HO
OH
OH
O
Ph
Ph
Ph
S
Ph
Ph
Ph
O
O
N
S
N
S
N
F
E
D
10 N. Wang, J. Wang, Y.-L. Guo, L. Li, Y. Sun, Z. Li, H.-X.
Zhang, Z. Guo, Z.-L. Li and X.-Y. Liu, Chem. Commun.,
2018, 54, 8885-8888.
Scheme 4 Proposed mechanism
11 (a) Y. Xu, Z. Wu, J. Jiang, Z. Ke and C. Zhu, Angew. Chem.
Int. Ed., 2017, 56, 4545–4548; (b) X. Tang and A. Studer,
Chem. Sci., 2017, 8, 6888–6892.
In summary, we have developed an iron-catalyzed acylation-
functionalization of unactivated alkenes with both aryl and
alkyl aldehydes via distal group ipso-migration. With this
strategy, the energy barrier and reversibility in the
difunctionalization of unactivated alkenes with nucleophilic
12
X. Tang and A. Studer, Angew Chem. Int Ed., 2018, 57,
814–817.
13 (a) T. Tachinami, T. Nishimura, R. Ushimaru, R. Noyori and
H. Naka, J. Am. Chem. Soc., 2013, 135, 50−53; (b) D. A.
Evans, D. J. Baillargeon and J. V. Nelson, J. Am. Chem. Soc.,
1978, 100, 2242−2244.
14 M. Ji, Z. Wu and C. Zhu, Chem. Commun., 2019, 55, 2368-
2371;
acyl radicals were well solved.
A wide range of β-
(hetero)arylated, -cyanated and -oximated unsymmetrical 1,6-
and 1,7-diketones were gained in moderate to good yields with
exclusive regioselectivity and chemoselectivity.
We gratefully acknowledge the National Natural Science
Foundation of China (21672259).
15
For selected reviews, see: (a) I. Bauer and H.-J. Knolker,
Chem. Rev., 2015, 115, 3170-3387; (b) R. Shang, L. Ilies
and E. Nakamura, Chem. Rev., 2017, 117, 9086-9139; (c)
C.-L. Sun, B.-J. Li and Z.-J. Shi, Chem. Rev., 2011, 111,
1293–1314; (d) F. Jia and Z. Li. Org. Chem. Front., 2014, 1,
194-214.
Conflicts of interest
There are no conflicts to declare
16 For selected reviews, see: (a) C. Chatgilialoglu, D. Crich, M.
Komatsu and I. Ryu, Chem. Rev., 1999, 99, 1991-2069; (b)
A. Banerjee, Z. Lei, M.-Y. Ngai, Synthesis, 2019, 51, 303-
333.
17 For selected examples, see: (a) W. Liu, Y. Li, K. Liu and Z.
Li, J. Am. Chem. Soc., 2011, 133, 10756-10759; (b) L. Lv, S.
Lu, Q. X. Guo and Z. Li, J. Org. Chem., 2015, 80, 698-704;
(c) L. Lv, H, Xi, X. Bai and Z. Li, Org. Lett., 2015, 17,
4324–4327; (d) L. Lv and Z. Li, Org. Lett., 2016, 18, 2264-
2267; (e) T. Tian, X. Wang, L. Lv and Z. Li, Eur. J. Org.
Chem., 2020, 4425–4428; (f) for a review, see: F. Jia and Z.
Li, Org. Chem. Front., 2014, 1, 194-214.
Notes and references
1
For selected reviews, see: (a) T. Pintauer and K.
Matyjaszewski, Chem. Soc. Rev., 2008, 37, 1087–1097; (b)
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DOI: 10.1039/D0CC06774A
O
R
OH
( )n
R1
Fe
O
( )n
R
+
FG
H
R1
(t-BuO)2
O
ipso-migration
FG
R, R1 = Aryl, heteroaryl, alkyl; n = 1 & 2
H
R1
HetAr
FG
=
N
N
OBn
Bn-oxime
heteroarenes
nitrile
Aryl and alkyl acyl radical feasible
synthesis of
unctionalized 1
diketones
,6- & 1,7-
One-pot
-f
β