-Catalyzed cascade arylation and chlorination of α-diazocarbonyl compounds with arylboronic acids and n -chlorosuccinimide for facile synthesis of α-aryl-α-chloro carbonyl compounds

Article abstract of DOI:10.1021/acs.orglett.5b00440

A Rh(III)-catalyzed cascade arylation and chlorination of α-diazocarbonyl compounds with arylboronic acids and N-chlorosuccinimide was achieved. The reaction exhibits excellent functional group tolerance on the organoboron and the diazo reagents; the functionalized α-aryl-α-chlorocarbonyl compounds were obtained in up to 86% yields. The cascade reaction should involve migratory carbene insertion of arylrhodium(III) to form some reactive rhodium(III)-diketonate complexes. Its subsequent reaction with N-chlorosuccinmide afforded the α-chlorocarbonyl products.

Full text of DOI:10.1021/acs.orglett.5b00440

Letter
pubs.acs.org/OrgLett
[RhIII(Cp*)]-Catalyzed Cascade Arylation and Chlorination of
α‑Diazocarbonyl Compounds with Arylboronic Acids and
N‑Chlorosuccinimide for Facile Synthesis of α‑Aryl-α-chloro Carbonyl
Compounds
Fo-Ning Ng, Yan-Fung Lau, Zhongyuan Zhou, and Wing-Yiu Yu*
State Key Laboratory for Chirosciences and Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic
University, Hung Hom, Kowloon, Hong Kong
S
* Supporting Information
ABSTRACT: A Rh(III)-catalyzed cascade arylation and
chlorination of α-diazocarbonyl compounds with arylboronic
acids and N-chlorosuccinimide was achieved. The reaction
exhibits excellent functional group tolerance on the organo-
boron and the diazo reagents; the functionalized α-aryl-α-chlorocarbonyl compounds were obtained in up to 86% yields. The
cascade reaction should involve migratory carbene insertion of arylrhodium(III) to form some reactive rhodium(III)−diketonate
complexes. Its subsequent reaction with N-chlorosuccinmide afforded the α-chlorocarbonyl products.
Scheme 1. Selected Examples for Intercepting σ-Alkyl/π-Allyl
Metal Complexes after Carbene Migratory Insertion
nalogous to carbon monoxide, migratory insertion of
Ametal−carbene complexes derived from diazo compounds
is attracting growing attention for transition-metal-catalyzed C−
C bond coupling reactions.1−4 Pioneered by van Vranken,2a−c
extensive investigation by Barluenga,2d,e Wang,2f,g Liang,2h,i and
our group7a,b showed that arylpalladium(II) would react with
diazo compounds to furnish palladium−carbene complexes,
which subsequently undergo migratory carbene insertion to
afford reactive σ-alkylpalladium(II) complexes. Owing to the
facile β-hydride elimination reactivity, attempts to bring about
further transformation(s) of the alkylpalladium(II) complexes
for formation of a second C−C/C−X bond have met with
limited success. Notably, Wang et al. successfully intercepted σ-
organopalladium after the migratory carbene insertion by
copper-acetylides, and cascade formation of two C−C bonds
was accomplished.5 Van Vranken et al. showed that π-
allylpalladium(II) complex formation after migratory carbene
insertion constitutes a fruitful strategy to effect three-component
coupling reactions (Scheme 1).6
Alternative to Pd catalysis, we7 accomplished the Rh(I)-
catalyzed three-component coupling reactions of arylboronates,
α-aryldiazoacetate, and alkyl halides.7e With [RhI(COD)Cl]2
(COD = 1,5-cyclooctadiene) as the catalyst and KOtBu as the
base, the coupling reaction afforded quaternary α,α-heterodiaryl
carboxylic acids in good yields. Mechanistically, the reaction is
likely mediated by diazo coupling with arylrhodium(I)
complexes to furnish oxa-π-allylrhodium(I) complexes. The
second C−C bond formation was achieved by SN2 displacement
with the alkyl halides after metathesis with KOtBu. Recently, we
achieved RhIII(Cp*)-catalyzed direct arene C−H insertion with
diazomalonates (Cp* = 1,2,3,4,5-pentamethylcyclopenta-
dienyl).7d This reaction involves diazo-malonate coupling with
arylrhodium(III) complexes as the principal step, and the
product σ-alkylrhodium(III) complex has been structurally
characterized. This alkylrhodium(III) would undergo proto-
nolysis for catalyst turnover with concomitant C−H bond
formation. Yet, it became clear that the alkylrhodium(III) would
undergo intramolecular N−O bond cleavage with benzohy-
droxamic acids as substrates, and C−N bond formation
resulted.3e,g,7c Thus, by exploiting the reactivity of the
alkylrhodium(III) complexes, we envisioned developing a
catalytic synthesis of quaternary stereocenters by cascade
difunctionalization on the carbene center with the formation of
C−C and C−X (X = halogen) bonds. Herein we report a
[RhIII(Cp*)]-catalyzed cascade arylation/chlorination of α-
diazocarbonyl compounds with arylboronic acids and N-
Received: February 11, 2015
Published: March 16, 2015
© 2015 American Chemical Society
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Organic Letters
Letter
chlorosuccimide (NCS) for the synthesis of α-aryl-α-chloro
carbonyl compounds.
= pinacol ester) (0.24 mmol) and KOtBu (0.24 mmol) as the
arylation reagent, 3aa was produced in <5% yield (entry 2). With
potassium phenyltrifluoroborate (PhBF3K) as the reagent, no
3aa formation was detected (entry 3). Interestingly, when boric
acid (0.2 mmol) was employed as an additive, the reaction with
PhBF3K (0.24 mmol) afforded 3aa in 63% yield (entry 4).
Notably, no 3aa was formed in the absence of [Rh(Cp*)(OAc)2]
(entry 5). Other Rh catalysts such as [Rh(Cp*)Cl2] and
[Rh(COD)OH]2 were found to be ineffective catalysts for the
chloroarylation (entries 6 and 7). Furthermore, [Ir(Cp*)Cl2]2,
[Cu(OAc)2], [CuCl], and [Pd(OAc)2] also did not effect any
catalytic chloroarylations (entries 8−11).
In this work, several common solvents such as toluene, DCE,
tBuOH, and DMA gave inferior results compared to DMF
(entries 12−15). Employing batchwise addition of either 1a
(0.08 mmol/h) or NCS (0.06 mmol/h) resulted in lower yields
(5% and 46%) of 3aa (entries 16 and 17). During our
optimization study, we observed a significant amount of dimethyl
mesoxalate formation in many cases. The mesoxalate was likely
derived from the reaction of diazomalonate, NCS, and residual
water.8 Gratifyingly, the mesoxalate formation can be suppressed
by employing more 1a (0.4 mmol) (entry 18). Under the
optimized conditions [1a (0.4 mmol), 2a (0.2 mmol), NCS (0.2
mmol), and [Rh(Cp*)(OAc)2] (5 mol %) in DMF at 40 °C for 6
h], 3aa can be obtained in 85% yield. Yet, other electrophilic
halogenation agents such as CuCl2, PhICl2, N-bromosuccinimde,
N-iodosuccinimide, and N-fluorobenzenesulfonimide were less
effective halogenation reagents, and the undesired hydro-
arylation products were formed dominantly (see Supporting
Informations).
We began by examining the hydroarylation reaction of
diazomalonate with arylboronic acids. Treating phenylboronic
acid (1a, 0.2 mmol) with methyl diazomalonate (2a, 0.2 mmol)
and [Rh(Cp*)(OAc)2] (5 mol %) in a dioxane−water mixture
(10:1, v/v) at rt for 6 h, α-phenyldimethylmalonate (3aa′) was
obtained in 90% yield. The hydroarylation reaction presumably
occurred via diazomalonate coupling with arylrhodiun(III)
complexes to furnish the rhodium(III)-enolates, which undergo
protonolysis to give the α-phenyldimethylmalonate. Encouraged
by this finding, we turned to examine the analogous
chloroarylation of diazomalonate with electrophilic chlorinating
reagents.
When 1a (0.24 mmol) reacted with 2a (0.2 mmol), N-
chlorosuccinimide (NCS; 0.2 mmol) and [Rh(Cp*)(OAc)2] (5
mol %) in dry DMF (1 mL) at 40 °C for 6 h, the desired dimethyl
α-phenyl-α-chloromalonate (3aa) was produced in 70% yield
(Table 1, entry 1). No hydroarylation products 3aa′ were
obtained. Other arylboronic acid derivatives were found to give
less satisfactory results. For instance, by employing PhBpin (pin
a
Table 1. Reaction Optimization
b
additives
(mmol)
3aa
entry
1
1
catalyst
solvent
DMF
(%)
PhB(OH)2 [Rh(Cp*)
−
70
<5
0
(OAc)2]
Scheme 2 depicts the substrate scope of the chloroarylation
reaction. With diazomalonate (2a) as the substrate, arylboronic
acids bearing ethereal, halogen, aldehyde, ketone, and ester
substituents were all tolerated with 3ba−3ha being obtained in
58−74% yields. Apparently, the analogous transformation with
2
3
4
PhBpin
[Rh(Cp*)
KOtBu
(0.24)
DMF
DMF
DMF
(OAc)2]
PhBF3K
PhBF3K
PhB(OH)2
[Rh(Cp*)
(OAc)2]
−
[Rh(Cp*)
(OAc)2]
B(OH)3
(0.2)
63
a
5
6
7
−
−
−
−
DMF
DMF
DMF
0
0
0
Scheme 2. Substrate Scope Studies
PhB(OH)2 [Rh(Cp*)Cl2]2
PhB(OH)2 [Rh(COD)
OH]2
8
PhB(OH)2 [Ir(Cp*)Cl2]2
AgSbF6
(0.02)
DMF
0
9
PhB(OH)2 [Cu(OAc)2]
PhB(OH)2 [CuCl]
−
DMF
DMF
DMF
toluene
0
0
0
0
10
11
12
Phen (0.04)
PhB(OH)2 [Pd(OAc)2]
−
−
PhB(OH)2 [Rh(Cp*)
(OAc)2]
13
14
15
PhB(OH)2 [Rh(Cp*)
−
−
−
−
−
−
DCE
0
25
(OAc)2]
PhB(OH)2 [Rh(Cp*)
tBuOH
DMA
DMF
DMF
DMF
(OAc)2]
PhB(OH)2 [Rh(Cp*)
5
(OAc)2]
c
16
PhB(OH)2 [Rh(Cp*)
5
(OAc)2]
d
17
PhB(OH)2 [Rh(Cp*)
46
(OAc)2]
e
18
PhB(OH)2 [Rh(Cp*)
(85)
(OAc)2]
a
Reaction conditions: phenylboronic acid or its derivatives (0.24
mmol), 2a (0.2 mmol), NCS (0.2 mmol), catalyst (5 mol %), additives
(0.02 mmol−0.24 mmol), dry DMF (1 mL) at 40 °C for 6 h under a
b
c
a
N2 atmosphere. NMR yields, isolated yield in parentheses. Batchwise
Reaction conditions: arylboronic acids (0.4 mmol), 2 (0.2 mmol),
d
addition of 1a (0.08 mmol/h). Batchwise addition of NCS (0.06
NCS (0.2 mmol), [Rh(Cp*)(OAc)2] (5 mol %), dry DMF (1 mL) at
40 °C for 6 h under a N2 atmosphere.
e
mmol/h). PhB(OH)2 (0.4 mmol) was employed.
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Letter
4-methoxyphenylboronic acid produced 3ca in a modest 30%
yield. It could be attributed by the competitive protodeboration
of the electron-rich arylboronic acids in the reaction mixture.
Other acceptor−acceptor diazo substrates were tested. For
instance, by subjecting diazoacetates bearing an amide group
(2d) and a phenylsulfonyl group (2e) to the chloroarylation
reaction [phenylboronic acid (0.4 mmol), NCS (0.2 mmol), and
[Rh(Cp*)(OAc)2] (5 mol %) in DMF at 40 °C for 6 h], the
desired 3ad and 3ae were produced in 60% and 53% yields.
Similarly, the analogous α-ketodiazoacetate (2b) was trans-
formed to 3bb in 73% yield with 4-bromophenylboronic acid
(1b) as a reagent. However, the reactions of cyclic diazo
compounds derived from Meldrum’s acid were unsuccessful, and
80% of the diazo starting material was recovered. When α-
phenyldiazoacetate was employed as the substrate, no chloroar-
ylation products were formed with methyl phenyloxoacetate
being isolated in 41% yield. The phenyloxoacetate was probably
produced by the competitive diazo oxidation with the NCS and
the residual moisture.8
Scheme 3. Synthesis of γ-Lactones by Cu-Catalyzed Radical
Cyclization
a
a
Reaction conditions: α-chlorocarbonyl compounds (0.1 mmol),
CuCl (30 mol %), 2,2′-bipyridine (30 mol %), DCE (5 mL) at 80
b
°C for 12 h under a N2 atmosphere. Combined yield of
diastereomers, and the absolute configuration of the individual
diastereomers were not determined.
According to the literature, rhodium−carbene complexes
would react with alkenes to afford cyclopropanes.9 In this work,
when diazoesters bearing a disubstituted CC bond were
employed for the RhIII-catalyzed chloroarylation, the desired 3af
(70%), 3ag (61%), and 3ah (65%) were obtained exclusively
without any cyclopropanes being formed. Similarly, diazoesters
bearing a more reactive trisubstituted CC bond were
transformed selectively to the corresponding α-chlorocarbonyl
compounds (3ai, 3bi, 3hi, 3bj, and 3bk) in 40−78% yields.
Assuming an arylrhodium(III) intermediate, these findings
suggested that migratory carbene insertion is kinetically more
competitive than intramolecular cyclopropanation.
To understand the mechanistic underpinning of the
chlorination step, we synthesized a well-defined rhodium(III)−
diketonate complex (5a). By reacting [Rh(Cp*)Cl2]2 (1 mmol)
and Na(α-phenylacetylacetone) (2 mmol) in acetone at rt for 12
h, 5a was isolated in 80% yield (Scheme 4). X-ray crystallo-
Scheme 4. Synthesis of Rhodium(III)−Diketonate Complex
5a and Its Reaction with NCS
Apparently, the migratory carbene insertion is more
competitive than carbenoid C−H insertion.10 For example,
when benzyl diazoacetylacetate (2c) reacted with 4-bromo-
phenylboronic acid (1b) for the chloroarylation reaction, the
desired α-chloroketone 3bc was isolated in 86% yield exclusively
(i.e., no benzylic/aryl C−H carbene insertion products were
obtained). Yet, thiophene groups are known to react with the
Rh−carbene complex to form reactive ylides,10 which would
undergo further transformations such as dipolar cycloaddition. In
this work, when 3-thienylboronic acid (1i) was treated with 2a
and NCS, the desired coupling product 3ia was furnished in 46%
yield selectively and no ylide-derived product was detected.
In this work, the functionalized α-chlorocarbonyl compounds
were further transformed into γ-lactones by the Cu-catalyzed
atom transfer radical cyclization.11 By treating α-chlorocarbonyl
compounds 3af with CuCl (30 mol %), 2,2′-bipyridine (30 mol
%) in DCE at 80 °C for 12 h, two 5-exo γ-lactones cis-4af and
trans-4af were obtained in 80% combined yields (cis-4af/trans-
4af = 1:1) (Scheme 3). The molecular structure of cis-4af was
established by X-ray crystallographic study, and the cis-
stereochemistry of the phenyl and 3-chloro alkyl group in cis-
4af was also confirmed. Similarly, α-chlorocarbonyl compounds
3ai, 3bi, and 3hi were converted to γ-lactones 4ai (76% yields),
4bi (86% yield), and 4hi (71% yield) by the Cu-catalyzed radical
cyclizations. However, radical cyclization for 3ag, 3ah, and 3bk
were unsuccessful; only the corresponding protodechlorination
side products were isolated. Interestingly, the reaction of α-
chlorocarbonyl compound 3bj did not give the expected 6-exo
cyclization product. Instead, the tandem radical cyclization/
radical aromatic C−H substitution occurred to afford a tricyclic
product 4bj in 22% yield (see Supporting Information).
graphic study established that the diketonate ligand binds nearly
symmetrically to the rhodium center through an O−O′-κ2
fashion: [Rh(1)−O(1): 2.0907 (14) Å vs Rh(1)−O(2): 2.0847
(15) Å ]. Complex 5a features a Rh(1)−O(1) bond distance of
2.0907 (14) Å, which is comparable to the corresponding
distance of the [Rh2III(Cp*)2(acac)2][BF4]2 complex Rh−
O(acac): [2.103 (4) Å].12 When 5a was treated with NCS in
DMF at 40 °C for 1 h, α-phenyl-α-chloroacetylacetone (6) was
formed in 40% yield (Scheme 4). This result suggested that the
rhodium(III)−diketonate complex is a likely intermediate for the
chlorination step.
A plausible reaction mechanism (Scheme 5) should involve
initial transmetalation of arylboronic acids to [Rh(Cp*)(OAc)2]
to afford the arylrhodium(III) complex A.13 A putative
arylrhodium−carbene complex B would undergo migratory
carbene insertion to the aryl group to furnish the rhodium(III)−
diketonate complex C. The chlorination step may be mediated by
prior coordination of the N-chlorosuccinimide to complex C,
followed by nucleophilic displacement of the N−Cl group by the
diketonate ligand.
To conclude, a Rh(III)-catalyzed cascade arylation and
chlorination of α-diazocarbonyl compounds with arylboronic
acids and N-chlorosuccinimide is developed. The reaction offers
a direct route to α-aryl-α-chlorocarbonyl compounds, which can
be converted to γ-lactones by Cu-catalyzed chlorine atom
transfer radical cyclizations. Preliminary mechanistic studies of
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Organic Letters
Letter
D. C.; Boultadakis-Arapinis, M.; Glouris, F. J. Am. Chem. Soc. 2013, 135,
12204. (g) Hyster, T. K.; Ruhl, K. E.; Rovis, T. J. Am. Chem. Soc. 2013,
135, 5364. See also ref 7.
Scheme 5. Plausible Reaction Mechanism
(4) Selected examples for the Cu-, Ni-, and Ir-catalyzed carbenoid
cross-coupling reactions: [Cu]: (a) Xiao, Q.; Xia, Y.; Li, H.; Zhang, Y.;
Wang, J. Angew. Chem., Int. Ed. 2011, 50, 1114. [Ni]: (b) Ni, Y.;
Montgomery, J. J. Am. Chem. Soc. 2006, 128, 2609. (c) Yu, Z.; Ma, B.;
Chen, M.; Wu, H.-H.; Liu, L.; Zhang, J. J. Am. Chem. Soc. 2014, 136,
6904. [Ir]: (d) Xia, Y.; Liu, Z.; Feng, S.; Zhang, Y.; Wang, J. J. Org. Chem.
2015, 80, 223.
(5) Zhou, L.; Ye, F.; Zhang, Y.; Wang, J. J. Am. Chem. Soc. 2010, 132,
13590.
(6) (a) Kudirka, R.; Devine, S. K. J.; Adams, C. S.; Van Vranken, D. L.
Angew. Chem., Int. Ed. 2009, 48, 3677. (b) Devine, S. K. J.; Van Vranken,
D. L. Org. Lett. 2008, 10, 1909. (c) Devine, S. K. J.; Van Vranken, D. L.
Org. Lett. 2007, 9, 2047.
(7) For our previous studies in carbenoid cross-coupling reactions,
[Pd]: (a) Tsoi, Y.-T.; Zhou, Z.; Chan, A. S. C.; Yu, W.-Y. Org. Lett. 2010,
12, 4506. (b) Yu, W.-Y.; Tsoi, Y.-T.; Zhou, Z.; Chan, A. S. C. Org. Lett.
2009, 11, 469. [Rh]: (c) Lam, H.-W.; Man, K.-Y.; Chan, W.-W.; Zhou,
Z.; Yu, W.-Y. Org. Biomol. Chem. 2014, 12, 4112. (d) Chan, W.-W.; Lo,
S.-F.; Zhou, Z.; Yu, W.-Y. J. Am. Chem. Soc. 2012, 134, 13565. (e) Tsoi,
Y.-T.; Zhou, Z.; Yu, W.-Y. Org. Lett. 2011, 13, 5370. For analogous
nitrene insertion: (f) Thu, H.-Y.; Yu, W.-Y.; Che, C.-M. J. Am. Chem. Soc.
2006, 128, 9048. (g) Ng, K.-H.; Chan, A. S. C.; Yu, W.-Y. J. Am. Chem.
Soc. 2010, 132, 12862. (h) Ng, K.-H.; Ng, F.-N.; Yu, W.-Y. J. Am. Chem.
Soc. 2012, 48, 11680.
the reaction showed that a rhodium-diketonate intermediate is
likely involved in the chlorination step.
ASSOCIATED CONTENT
* Supporting Information
■
S
Detailed experimental procedures, analytical data, and copies of
NMR spectra of the products. This material is available free from
charge via the Internet at http://pubs.acs.org.
(8) For the analogous diazo oxidation, see: Roßbach, J.; Baumeister, J.;
Harms, K.; Koert, U. Eur. J. Org. Chem. 2013, 662.
(9) Selected reviews for Rh(II)-catalyzed cyclopropanation reactions:
(a) Wang, H.; Guptill, D. M.; Varela-Alvarez, A.; Musaev, D. G.; Davies,
H. M. L. Chem. Sci. 2013, 4, 2844. (b) Doyle, M. P.; Forbes, D. C. Chem.
Rev. 1998, 98, 911. Selected examples for Rh(I)-catalyzed cyclo-
propanation reactions: (c) Demonceau, A.; Simal, F.; Noels, A. F.
Tetrahedron Lett. 1997, 38, 7879. (d) Nishimura, T.; Maeda, Y.; Hayashi,
T. Angew. Chem., Int. Ed. 2010, 49, 7324.
(10) (a) Doyle, M. P.; McKervey, M.; Ye, T. Modern Catalytic Methods
for Organic Synthesis with Diazo Compounds; Wiley: New York, 1998.
For an example of Rh(I)-catalyzed carbenoid C−C bond insertions:
(b) Xia, Y.; Liu, Z.; Liu, Z.; Ge, R.; Ye, F.; Hossain, M.; Zhang, Y.; Wang,
J. J. Am. Chem. Soc. 2014, 136, 3013. Ylide transformations: (c) Ma, X.;
Jiang, J.; Lv, S.; Yao, W.; Yang, Y.; Liu, S.; Xia, F.; Hu, W. Angew. Chem.,
Int. Ed. 2014, 53, 13136.
(11) The reaction conditions for the Cu-catalyzed atom transfer radical
cyclizations: (a) Yang, D.; Yan, Y.-L.; Zheng, B.-F.; Gao, Q.; Zhu, N.-Y.
Org. Lett. 2006, 8, 5757. For selected examples in atom transfer radical
cyclizations, see: (b) Yang, D.; Gu, S.; Yan, Y.-L.; Zhao, H.-W.; Zhu, N.-
Y. Angew. Chem., Int. Ed. 2002, 41, 3014. (c) Curran, D. P.; Chang, C. T.
J. Org. Chem. 1989, 54, 3140. (d) Curran, D. P.; Chen, M. H.; Spletzer,
E.; Seong, C. M.; Chang, C. T. J. Am. Chem. Soc. 1989, 111, 8872.
(12) Rigby, W.; Lee, H.-B.; Bailey, P. M.; McCleverty, J. A.; Maitlis, P.
M. J. Chem. Soc., Dalton Trans. 1979, 387.
AUTHOR INFORMATION
Corresponding Author
■
*E-mail: wing-yiu.yu@polyu.edu.hk.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
We thank The Hong Kong Research Grants Council
(PolyU503811P) for financial support.
■
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