Nickel-catalyzed intramolecular desymmetrization addition of aryl halides to 1,3-diketones

Article abstract of DOI:10.1039/d0cc00457j

A nickel-catalyzed intramolecular addition of aryl halides to 1,3-diketones was first developed. This desymmetrization reaction afforded polycyclic products bearing two tetrasubstituted centers with excellent diastereoselectivities and high yields. Moderate enantioselectivities were achieved in the presence of a chiral ligand. This transformation has great potential for the synthesis of polycyclic compounds including spiro[4,4,3,0] compounds. This journal is

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DOI: 10.1039/D0CC00457J
Journal Name
EDGE ARTICLE
Nickel-catalyzed Intramolecular Desymmetrization Addition of
Aryl Halides to 1,3-Diketones
Pan Zhou and Tao XU*
Received 00th January 20xx,
Accepted 00th January 20xx
A nickel-catalyzed intramolecular addition of aryl halides to 1,3-diketones was first developed. This desymmetrization
reaction afforded polycyclic products bearing two tetrasubstituted centers with excellent diastereoselectivities and high
yields. Moderate enantioselectivities were achieved in the presence of a chiral ligand. This transformation has great
potential for the synthesis of polycyclic compounds including spiro[4,4,3,0] compounds.
DOI: 10.1039/x0xx00000x
www.rsc.org/
Polycyclic frameworks with tetrasubstituted carbons, including was generated in situ from an arylboronic acid with an alkyne,
tertiary alcohols and all-carbon quaternary centres, are to the carbonyl site (eq 2, scheme 1).9 Although enantioselective
widespread in natural products, organic materials, and desymmetrization Heck or Michael reactions initiated from aryl
synthetic biologically active molecules (figure 1).1 It has or vinyl halides have been developed,10 the desymmetrization
attracted many efforts towards exploring convenient and addition of aryl halides to diketones has not been disclosed.
efficient protocols to access such frameworks, especially the
Previous work:
construction of stereospecific quaternary centers.2 In particular,
R'
desymmetrization reactions have received much attention
recently because of their numerous advantages for the
construction of multi-chiral quaternary carbon centres as well
as bicyclic skeletons with high stereoselectivities.3
O
Pd
O
R'
(eq 1)
(eq 2)
ketone -arylation
O
R
O
Br
R
O
Ar1
OH
O
Ar1
O
Ni
OH
Br
O
H
H
ketone addition
in situ 'vinyl-Ni'
Ar2
H
+
Me
O
Ar2B(OH)2
H
H
H
HO
O
HO
OH
Antitumor agent
This work:
Hamigeran B
(+)-Estrone
O
R'
HO
Ni
R'
R
n
(eq 3)
Figure 1 Selected Examples with Bicycle Skeletons in Natural Products and
Drugs.
n
ketone addition
O
R
Br
'aryl-Ni'
n = 1,2
O
Cyclic symmetric 1,3-diketones with two different
substituents at the prochiral carbon are one of the most useful
scaffolds to demonstrate the power of desymmetrization, such
as the Hajos-Parrish reaction.4 Transition-metal catalysts are
often used to improve the efficiencies and selectivities of
desymmetrization reactions.5 Although many transformations
involving C(sp3)-metal intermediates with a 1,3-diketone
partner have been reported, reactions with C(sp2)-metal
species have not been studied comprehensively.6-7 In 2017,
Shi’s group published an enantioselective palladium-catalyzed
ketone α-arylative desymmetrization of 1,3-diketones (eq 1,
scheme 1).8 Besides, Lam and co-workers reported a nickel-
catalyzed addition reaction of a vinyl-nickel intermediate, which
Scheme 1 The Desymmetrization Reactions with Vinyl-metal Intermediates.
The addition pathway of an aryl framework to ketones is a
convenient route to access tertiary benzylic alcohols and usually
relies on organometallic reagents, such as Grignard or
organozinc reagents11. These methods are widely used because
of the ready availability of aryl halide materials but also face
some issues when sensitive functional groups are involved.
Therefore, efforts are taken to develop a superior alternative
where aryl halides are directly employed in the presence of a
transition metal catalyst and reductant.12-13 This approach can
efficiently avoid the use of dangerous organometallic reagents
with low functional group tolerance. For example, the
palladium-catalyzed addition of aryl bromides to ketones was
reported by Yamamoto et al in 2000.14 Recently, Kündig’s and
Jia’s groups reported the reaction of aryl halides or vinyl
bromides with α-ketoamides.15 Considering the potential of
Shanghai Key Laboratory of Chemical Assessment and Sustainability, School of
Chemical Science and Engineering, Tongji University, 1239 Siping Road, Shanghai,
200092, P. R. of China.
E-mail: taoxu@tongji.edu.cn.
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merging desymmetrization and ketone addition strategies to carbon centre of 1,3-diketone part. A variety of functional
View Article Online
DOI: 10.1039/D0CC00457J
extend chiral tetrasubstituted carbons, herein, we report a groups such as alkyl
nickel-catalyzed addition of aryl halides to 1,3-diketones to
Table 1 Optimizations on Ni-catalyzed Intramolecular Desymmetrization
access the bicyclic[m.n.0] skeleton with high yields and
Addition of Aryl Halide to 1,3-Diketone.a
excellent diastereoselectivities (eq 3, scheme 1). In addition, the
HO
O
enantioselective desymmetrization of this transformation is
investigated to give two stereospecific tetrasubstituted carbon
centres with moderate enantioselectivities in the presence of a
chiral ligand.
General condtionsa
2,2'-bipyridine (ligand)
Mn, DMA, 50oC,8-12h
R
R
O
Br
1a
1b
O
2a
(±)- R = Me
R = Me
R = Bn
2b
(±)- R = Bn
We commenced this study with 2-(2-bromobenzyl)-2-
methylcyclohexane-1,3-dione (1a) as a model substrate, under
the conditions with nickel as a catalyst, and metal dust as the
reductant (table 1). After carefully evaluations of ligands,
reductants, and solvents (for details, see supporting
information (SI)), we were delighted to find that product 2a can
be afforded in very high yield and excellent diastereoselectivity
(dr >20:1) under these conditions as illustrated in entry 1, Table
1. The yield decreased a little bit when conducting at room
temperature (entry 2) or lower catalyst loading (entry 3). Other
Entry
1
Substrate
1a
Catalyst
Ni(cod)2
Ni(cod)2
Ni(cod)2
Ni(cod)2
Ni(cod)2
FeBr3
Yield
(±)-2a(>99%)
(±)-2a(95%)
(±)-2a(98%)
(±)-2a(72%)
(±)-2a(70%)
n.r.
n.r.
n.r.
(±)-2a(27%)
n.r.
n.r.
n.r.
(±)-2b(46%)
(±)-2b(84%)
(±)-2b(>99%)
n.r.
2b
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1b
1b
1b
1b
3c
4d
5e
6
7
8
9
10
11f
12g
13
14h
15i
16
CoBr2
Cu(OTf)2
Pd(OAc)2
---
Ni(cod)2
Ni(cod)2
Ni(cod)2
Ni(cod)2
Ni(cod)2
---
ligands,
such
as
1,10-phenanthroline,
1,2-
bis(diphenylphosphino)ethane, were also suitable but with
lower yields (entries 4 and 5). Other catalysts, such as FeBr3,
CoBr2, and Cu(OTf)2, didn’t afford the desired products, while
palladium acetate only gave a poor conversion (entries 6-9).
Additionally, control experiments showed that the nickel
catalyst, ligand, and reductant were all crucial to the ketone
addition reaction (entries 10-12).
a
General conditions: 1 (0.1 mmol), catalyst (5 mol%), 2,2’-bipyridine (10
mol%), Mn (0.2 mmol), DMA (1.0 mL), 50oC, 8-12 h; yields and ratios (dr
However, when the benzyl substituted substrate 1b was >20:1) were determined by NMR by using CH2Br2 as the internal standard. b
c
d
At room temperature. Ni(cod)2 (2 mol%), 1,1-bipyridine (5 mol%). 1,10-
phenanthroline (10 mol%) as ligand. e 1,2-bis(diphenylphosphino)ethane (10
mol%) as ligand. f Without ligand. g Without Mn. h NaI (0.2 mmol) was added
as additive. i MgCl2 (0.2 mmol) was added as additive.
employed, the only moderate yield was detected (entry 13,
table 1). To improve the yield, various additives were studied.
The reaction gave 84% and 99% yields in the presence of 2
equivalent of NaI or MgCl2, respectively (entries 14 and 15).
MgCl2 was often employed to improve the yields in reductive
coupling reactions and believed to facilitate the reduction of the
metal complex by Zn or Mn to generate active metal catalysis.16
Meanwhile, the Lewis acidity of MgCl2 may further active the
carbonyl group to favour the addition step17, as ZnBr2 in the
aldehyde addition demonstrated by Weix group13b. However,
the exact role of MgCl2 still remains elusive. The nickel catalyst
was also indispensable under these conditions as well (entry 16).
With the optimal conditions in hand (entry 15, table 1), we
next explored the scope of this transformation (representative
examples were summarized in table 2). In general, the
(2j, 2l), sulfur ether (2k), benzyl (2b, 2m), were well tolerated.
Importantly, heterocyclic structures consisting of furan (2n) and
thiophene (2o) were also suitable substrates. The substituents
on the 1,3-diketones framework have no obvious effect on the
yield (2p).
To our surprise, when compound 1q was used in the reaction,
besides the normal product 2q (17%), another spiro[4,4,3,0]
compound
diastereoselectivity, which was possibly produced through the
desymmetrization addition following by a formal intramolecular
transesterification process. The yield of this spiro compound
increased to 69% yield in the presence of KOH as an additive
(eq. 4).19
To further study the scopes, some other types of substrates
were studied. It was found that as well as the cyclohexane-1,3-
diketones, substituted cyclopentane-1,3-diketone substrates
also afforded the desired products under the conditions (5a, eq.
5). In addition, the scope of this desymmetrization reaction
3 was obtained in 36% yield with high
substrates with either electron-neutral, -donating or
-
withdrawing substituents, as well as groups on various positions
of aryl part, can proceed smoothly to access the corresponding
products in high yields and excellent diastereoselectivities
(>20:1 dr). The syn configuration was confirmed by X-ray
crystallography using compound 2a (figure 2)18. The reaction on
1 mmol scale gave a moderate yield. The aryl iodide substrate
can also be used but aryl chloride didn’t form any target
product. The alkyl substituents on the aryl group did not
significantly affect the reactivity (2c, 2d), even in the adjacent
site (2c). The aryl fluoride or chloride groups (2e-2g), the
methoxide (2k, 2i) can survive under these nickel-catalyzed
reactions. More investigations were focused on the quaternary
2 | J. Name., 2020, 00, 1-3
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improve the yield, MgCl2 was added. However, VtiehweArrtieclaecOtniloinne
DOI: 10.1039/D0CC00457J
showed no enantioselectivity then. The use of a ligand L3 in the
HO
mixed solvents could give a better yield and moderate
enantioselectivity synchronously. Under these conditions,
moderate yields and enantioselectivities were obtained with
some tested samples as shown in Table 3.
O
2a
(±)-
O
Figure 2 The X-ray Crystallography of Compound 2a.
O
O
'standard condition'
Table 2 Scopes on Ni-catalyzed Intramolecular Desymmetrization Addition of
Aryl Halides to 1,3-Diketone. a
(eq. 4)
O
Br
R''
O
O
1q
3
(±)-
+
O
R'
OtBu
Ni(cod)2 (5 mol%)
2,2'-bipyridine (10 mol%)
R''
HO
R'
R
without KOH
(±)- 36%
3
(±)-
2q
17%
R''
R''
with KOH (2 equiv.)
(±)- 69%
3
Mn (2 equiv.), MgCl2 (2 equiv.)
DMA (0.1 M), 50oC, 8 -12 h
R
O
Br
HO
O
O
'standard condition'
1
2
(eq. 5)
(eq. 6)
(eq. 7)
(±)- (>20:1 dr)
HO
O
HO
HO
HO
Br
O
4a
4b
5a
(±)- 79% (>20:1 dr)
O
Ni(cod)2 (10 mol%)
2,2'-bipyridine (15 mol%)
O
O
O
O
HO
Ph
O
2b
2c
2d
(±)- 89%
(±)- 86%
(±)- 70%
2a
(±)- 96%
(68%b), 78%c))
Mn (2 equiv.), MgCl2 (2 equiv.)
DMA (0.1 M), 50oC, 8 h
Br
O
5b
(±)- 67% (>20:1 dr)
O
Cl
F
HO
HO
HO
HO
O
HO
F
'standard condition'
O
O
O
O
O
O
(±)- 83% (3:1 dr)
2e
2f
2g
2h
(±)- 77%
(±)- 79%
(±)- 81%
(±)- 76%
Br
O
4c
5c
HO
HO
HO
O
HO
T
able 3 Preliminary Results on Asymmetric Ni-catalyzed Intramolecular
Addition Reaction.a
O
O
O
Ni(cod)2 (10 mol%)
Chiral ligand (15 mol%)
O
HO
S
O
Mn (2 equiv.)
DMA (0.1 M), 25-30oC, 8 -12 h
2i
2j
2k
2l
(±)- 58%
(±)- 76%
(±)- 48%
(±)- 54%
O
Br
O
HO
HO
HO
1a
2a
HO
PPh2
O
O
O
N
O
O
Fe
N
N
O
R
O
S
R
MeO
i
i
L1
L2
: R = Pr:
74%; 75:25 er
42%; 70:30 er
27%; 92:8 er
84%; 50:50 er
L3
L4
: R = Pr
82%; 75:25 er
84%; 71:29 er
76%; 80:20 er
86%; 50:50 er
2m
2n
(±)- 62%
2o
(±)- 57%
2p
(±)- 63%
(±)-
93%
: R = Ph:
: R = Ph
aGeneral conditions: 1 (0.2 mmol), Ni(cod)2 (5 mol%), 2,2’-bipyridine (10
mol%), Mn (0.4 mmol), MgCl2 (0.4 mmol), DMA (2.0 mL), 50oC, 8-12 h;
isolated yields were given. For all tested samples, the products with >20:1 dr
bL1
cL1
: R = Pr:
bL3
i
i
: R = Pr
: R = Pr:
b,cL3
i
i
: R = Pr
were found by 1H NMR of crude mixture. On 1 mmol scale. Aryl iodide
b
c
HO
HO
HO
HO
substrate was used.
could be extended to prepare products with [4,4,0] skeletons in
high yield by increasing the carbon linker number (5b, eq. 6).
Interestingly, an acyclic substrate was also effective to construct
O
O
O
O
Ph
d
d
d
d
2a
2b
2c
2l
76%
32%
65%
67%
a
multi-substituted 2,3-dihydro-1H-indene although the
80:20 er
90:10 er
81:19 er
74:26 er
diastereoselectivity was not as high as that obtained for the
cyclic substrates (5c, eq. 7).
a General conditions: 1a (0.1 mmol), Ni(cod)2 (10 mol%), chiral ligand (15 mol%),
Mn (0.2 mmol), DMA (1.0 mL), 25-30oC, 8-12 h; yields and ratios (dr >20:1) were
determined by NMR by using CH2Br2 as the internal standard, the ee values were
To investigate the enantioselective transformation of this
reaction, some preliminary efforts were taken on the
asymmetric reaction. Considering the oxazoline ligands were
widely used in the nickel-catalyzed reactions, this type of ligand
was studied. The use of a chiral ligand L1 or L3 could give 75:25
er. Similar results were obtained in the presence of L2 or L4. The
product was afforded in 92:8 er with L1 as a ligand in the mixed
DMA / 1,4-dioxane solvent but the yield was very low. To
b
determined by chiral HPLC analysis. DMA/1,4-dioxone (v/v 4/1) was used as
solvent. c MgCl2 (0.2 mmol) was added as additive. d Isolated yield was given and
the absolute stereochemistry was not determined.
The bicycle product 2a obtained by this method was used to
demonstrate the synthetic utility of this methodology (scheme
2). The carbonyl group can be reduced by NaBH4 to give the
alcohol product (6a) with high diastereoselectivity. The epoxy
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EDGE ARTICLE
Journal Name
4
5
6
(a) Z. G. Hajos, D. R. Parrish, Patent, 1971, DE 2102623. (b) U.
Eder, G. Sauer, R. Wiechert, Angew. Chem., Int.VEiedw.A1rt9ic7le1O,n1lin0e,
496-497. (c) S. Prévost, N. Dupré, M.DLOeIu: t1z0s.1c0h3,9Q/D.0WCCa0n0g4,57VJ.
Wakchaure, B. List, Angew. Chem., Int. Ed. 2014, 53, 8770-
8773.
(a) Q. Gong, J. Wen, X. Zhang, Chem. Sci. 2019, 10, 6350-3653.
(b) B. Shi, S. Merten, D. K. Y. Wong, J. C. K. Chu, L. L. Liu, S. K.
Lam, A. Jäger, W.-T. Wong, P. Chiu, P. Metz, Adv. Synth. Catal.
2009, 351, 3128-3132. (c) B. M. Partridge, J. SolanaꢀGonzález,
H. W. Lam, Angew. Chem., Int. Ed. 2014, 53, 6523-6527.
(a) B. M. Bocknack, L.-C. Wang, M. J. Krische, Proc. Natl. Acad.
Sci. U.S.A. 2004, 101, 5421-5424. (b) A. R. Burns, J. Solanaꢀ
González, H. W. Lam, Angew. Chem., Int. Ed. 2012, 51, 10827-
10831. (c) J. Deschamp, O. Riant, Org. Lett. 2009, 11, 1217-
1220. (d) J. Ou, W.-T. Wong, P. Chiu, Org. Biomol. Chem. 2012,
10, 5971-5978.
unit was installed by Me3SI with high dr and good yield. The
Wittig reaction can be employed to synthesize the olefin
product (6c). Also, the tertiary alcohol can be transformed into
the internal alkene product (6d) in the presence of p-TsOH.
HO
HO
NaBH4
Me3S+I-
THF
THF/MeOH
O
OH
HO
6a
6b
(±)- 78%
(±)- 91%
O
2a
HO
Ph3P+MeBr-
THF
p-TsOH
Toluene
O
7
8
9
P. Zheng, X. Han, J. Hu, X. Zhao, T. XU, Org. Lett. 2019, 21,
6040-6044.
C. Zhu, D. Wang, Y. Zhao, W.-Y. Sun, Z. Shi, J. Am. Chem. Soc.
2017, 139, 16486-16489.
C. Clarke, C. A. Incerti-Pradillos, H. W. Lam, J. Am. Chem. Soc.
2016, 138, 8068-8071.
6c
(±)- 78%
6d
(±)- 58%
Scheme 2 Derivatization of Bicyclic Product 2a.
Conclusions
10 For some selected samples, see: (a) T. Ohshima, K. Kagechika,
M. Adachi, M. Sodeoka, M. Shibasaki, J. Am. Chem. Soc. 1996,
118, 7108-7116. (b) Y. Sato, M. Sodeoka, M. Shibasaki, J. Org.
Chem. 1989, 54, 4738-4739. (c) P. Liu, Y. Fukui, P. Tian, Z.-T.
He, C.-Y. Sun, N.-Y. Wu, G.-Q. Lin, J. Am. Chem. Soc. 2013, 135,
11700-11703.
11 For some selected reviews, see: (a) Y.-L. Liu, X.-T. Lin, Adv.
Synth. Catal. 2019, 361, 876-918. (b) J. F. Collados, R. Solà, S.
R. Harutyunyan, B. Maciá, ACS Catal. 2016, 6, 1952-1970. (c)
J. Rong, T. Pellegrini, S. R. Harutyunyan, Chem. Eur. J. 2016,
22, 3558-3570.
12 For some selected samples, see: (a) R. Shi, X. Hu, Angew.
Chem., Int. Ed. 2019, 58, 7454-7458. (b) H. Chen, X. Jia, Y. Yu,
Q. Qian, H. Gong, Angew. Chem., Int. Ed. 2017, 56, 13103-
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Cherney, S. E. Reisman, J. Am. Chem. Soc. 2017, 139, 5684-
5687.
In summary, we have reported
a
nickel-catalyzed
intramolecular addition of aryl halides to ketones, which
produced a polycyclic framework with two tetrasubstituted
carbons in excellent diastereoselectivity. Further attempts of
the
asymmetric
reaction
achieved
moderate
enantioselectivities. This novel desymmetrization reaction
exhibits excellent functional group tolerance and high potential
synthetic utility. Using this method, a spiro[4,4,3,0] compound
could be easily obtained in good yield.
Conflicts of interest
The authors declare no competing financial interest.
13 For some reactions on aldehyde addition, see: (a) K. K.
Majumdar, C.-H. Cheng, Org. Lett. 2000, 2, 2295-2298. (b) K.
J. Garcia, M. M. Gilbert, D. J. Weix, J. Am. Chem. Soc. 2019,
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Yamaguchi, A. Itoh, Eur. J. Org. Chem. 2019, 7483-7487.
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Gao, Y.-X. Jia, Tetrahedron Lett. 2014, 55, 2805-2808. (b) J.-X.
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Acknowledgements
We thank NFS of China (Grants 21801188), Shanghai Pujiang
Program, the “1000 Youth Talents Plan”, the Fundamental
Research Funds for the Central Universities and Tongji
University for financial support. We thank Dr. Natasha Lundin
for polishing the manuscript.
Notes and references
16 For some selected samples, see: (a) Y. Ye, H. Chen, J. L. Sessler,
H. Gong, J. Am. Chem. Soc. 2019, 141, 820-824. (b) H. Chen, X.
Jia, Y. Yu, Q. Qian, H. Gong, Angew. Chem., Int. Ed. 2017, 56,
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2
3
18 CCDC-1951717 contains the supplementary crystallographic
data for this paper [2a]. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
(a) X.-P. Zeng, Z.-Y. Cao, Y.-H. Wang, F. Zhou, J. Zhou, Chem.
Rev. 2016, 116, 7330-7396. (b) K. S. Petersen, Tetrahedron
Lett. 2015, 56, 6523-6535.
4 | J. Name., 2020, 00, 1-3
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19 KOH could be
EDGE ARTICLE
a
promoter for the intramolecular
View Article Online
transesterification. For some literatures, see: (a) P.-Q. Huang,
H. Geng, Chem. Sci. 2018, 20, 593-599. (b) M. J. Batchelor, R.
J. Gillespie, J. M. C. Golec, C. J. R. Hedgecock, S. D. Jones, R.
Murdoch, Tetrahedron 1994, 50, 809-826.
DOI: 10.1039/D0CC00457J
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