Nickel-catalyzed: Exo -selective hydroacylation/Suzuki cross-coupling reaction

Article abstract of DOI:10.1039/c9cc07558e

The first nickel-catalyzed intramolecular hydroacylation/Suzuki cross coupling cascade of o-allylbenzaldehydes with a broad range of phenylboronic acid neopentyl glycol esters has been developed. This strategy shows high regioselectivity and step economy in the construction of two C-C bonds via aldehyde C-H bond activation, affording valuable indanones with high efficiency.

Full text of DOI:10.1039/c9cc07558e

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Nickel-catalyzed exo-selective hydroacylation/
Suzuki cross-coupling reaction†
Cite this: Chem. Commun., 2019,
55, 14984
Shao-Chi Lee,a Lin Guoa and Magnus Rueping
*
ab
Received 26th September 2019,
Accepted 15th November 2019
DOI: 10.1039/c9cc07558e
rsc.li/chemcomm
The first nickel-catalyzed intramolecular hydroacylation/Suzuki
We therefore aimed at developing a nickel-catalyzed intra-
cross coupling cascade of o-allylbenzaldehydes with a broad range molecular hydroacylation/Suzuki cross coupling domino reaction10
of phenylboronic acid neopentyl glycol esters has been developed. which allows the synthesis of different substituted indanones.11
This strategy shows high regioselectivity and step economy in the
construction of two C–C bonds via aldehyde C–H bond activation, nucleophilic coupling partners due to their stability, straight-
Based on our recent work,12 boronates were selected as
affording valuable indanones with high efficiency.
forward manipulation, and excellent functional group tolerance
in transition-metal catalyzed cross coupling reactions. More-
Hydroacylation is an effective reaction enabling the functiona- over, in a recent publication, an in situ generated s-alkyl-Ni(II)
lisation of formyl C–H bonds with unsaturated C–C bonds, species was proposed to undergo Suzuki cross coupling with
which has attracted growing attention due to its facile and organoborons.13 Herein, we report the first nickel-catalyzed exo-
straightforward manner in synthesizing various carbonyl selective intramolecular hydroacylation/Suzuki cross coupling
structures.1 Following the initial hydroacylation,2 protocols domino reaction for the construction of a variety of substituted
regarding the control of stereo-3 and enantioselectivity,4 the indanones. Notably, an additional hydride acceptor is unexpectedly
synthesis of macro-5 and heterocycles,6 as well as related not required in this protocol.
mechanistic studies7 have been published. Among the transi-
2-Allylbenzaldehyde (1a) and phenylboronic acid neopentyl
tion metals used, rhodium, ruthenium, cobalt and nickel were glycol ester (2a) were used for evaluating the nickel-catalyzed
found to be effective for the inter- and intramolecular hydro- exo-selective intramolecular hydroacylation/Suzuki cross-coupling
acylation of alkenes and alkynes.1 Regarding the application domino reaction (Table 1). Our preliminary investigation was per-
of nickel based catalysts in intramolecular hydroacylation formed with Ni(cod)2, 1,3-bis-(2,6-diisopropylphenyl)imidazolium
reactions the cyclization of o-allylbenzaldehydes has been chloride (IPrꢀHCl) and cesium fluoride in toluene at 130 1C,
reported and the mechanism has been supported by the providing the desired indanone product 3a in 25% GC yield after
isolation of key intermediates (Scheme 1a).8 Subsequently,
triethylsilane was shown to achieve silyl-protected 1-indanol
products (Scheme 1b).9 Thus, both strategies lead to the
generation of products bearing methyl groups at the generated
tertiary/quaternary carbon centre. The feasibility of promoting
an intramolecular acylation reaction with subsequent cross
coupling reaction, leading to products bearing various substitu-
ents in the a-position to the carbonyl group (Scheme 1c) has not
been demonstrated yet.
a Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074,
Aachen, Germany. E-mail: magnus.rueping@rwth-aachen.de
b KAUST Catalysis Center (KCC), King Abdullah University of Science and
Technology (KAUST), Thuwal 23955-6900, Saudi Arabia
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
Scheme 1 Hydroacylation/Suzuki domino cross-coupling.
c9cc07558e
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Table 1 Optimization of the exo-selective intramolecular hydroacylation/
Suzuki cross-coupling domino reactiona
Table 2 Substrate scope of arylboronic acid neopentyl glycol esters and
benzaldehydesa
Entry
Change from standard conditions
Yieldb (%)
1
2
3
None
80 (75)c
25
28
CsF instead of Cs2CO3 and H2O
Without H2O
4
5
6
7
8
9
10
11
12
13
SIPrꢀHCl instead of IPrꢀHCl
IMesMeꢀHBF4 instead of IPrꢀHCl
Phenylboronic acid instead of 2a
NiCl2 instead of Ni(cod)2
Pd(OAc)2 instead of Ni(cod)2
Xylene instead of toluene
110 1C instead of 130 1C
36 h instead of 16 h
68
28
30
o10
0
35
56
78
Trace
Trace
Without Cs2CO3
Without Ni(cod)2
a
Reaction conditions: 1a (0.2 mmol), 2 (0.6 mmol), [M] (5 mol%),
ligand (10 mol%), base (2 equiv.), H2O (5 equiv.), toluene (1 ml) at
b
c
130 1C, 16 h. GC yields, decane as internal standard. Yield after
isolation.
16 h (entry 2). Using Cs2CO3 as base afforded indanone 3a in
28% yield (entry 3). The main side product of the reaction was
found to be 2-methyl-2,3-dihydro-1H-inden-1-one, the product
from intramolecular hydroacylation with subsequent reductive
elimination (vide infra, Scheme 3). Accordingly, we hypothesized
that the yield of the desired reaction could be increased if the
hydride from the nickel-complex F is transferred and the unde-
sired reductive elimination is effectively avoided.
To our surprise, an improved GC yield of 80% (75% yield
after isolation, entry 1) was obtained in the absence of any
hydride acceptor but presence of water in the reaction system.
Since ligands typically play a decisive role in catalytic reactions,
we further monitored the effect of ligand. IPrꢀHCl was replaced by
1,3-bis(2,6-diisopropylphenyl)-imidazolidinium chloride (SIPrꢀHCl)
and 1,3-bis(2,4,6-trimethylphenyl)-4,5-dimethyl-imidazolium tetra-
fluoroborate (IMesMeꢀHBF4), yet they afforded unsatisfying results
(entries 4 and 5). Next, another boron source, phenylboronic acid,
was examined, however, a lower yield was detected (entry 6). With
nickel(II) chloride and palladium(II) acetate as alternative catalysts
only poor yield or no desired product was obtained (entries 7 and
8). Changing the solvent to xylene provided an unsatisfactory yield
(entry 9). In addition, neither decreasing the temperature (entry 10),
nor extending the reaction time (entry 11) offered beneficial results.
Finally, control experiments revealed that the desired product
a
Reaction conditions: 1 (0.2 mmol), 2 (0.6 mmol), Ni(cod)2 (5 mol%),
IPrꢀHCl (10 mol%), Cs2CO3 (2 equiv.), H2O (5 equiv.), toluene (1 ml) at
130 1C, 16 h. Yields after isolation.
formation was not achieved without base or nickel catalyst (entries hydroacylation/Suzuki cross-coupling domino reaction with
12 and 13).
With the optimal reaction conditions in hand, we next evalu-
respect to various arylboronic acid neopentyl glycol esters.
As shown in Table 2, a wide range of boronic esters could be
ated the scope of this newly developed exo-selective intramolecular converted into the appropriate products in moderate to high
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Next, we had a closer look at our intramolecular hydroacylation/
Suzuki cross-coupling domino reaction. In order to gain a better
understanding of the catalysis we examined two additional reac-
tions (Scheme 2). When deuterated aldehyde 4 was reacted with
boronic acid neopentylglycol ester 2a in the absence of water, the
deuterated product 5 was isolated (Scheme 2a). In addition,
subjecting indenol 6 to our standard reaction conditions led to
the corresponding oxidized product 7 in 53% yield (Scheme 2b).
These results, while preliminary, suggest more than one possible
reaction pathway for the intramolecular hydroacylation/Suzuki
cross-coupling reaction.
Scheme 2 Investigation of the reaction mechanism.
Based on our observations and our previous studies,15 we
propose the following mechanism for this exo-selective intra-
yields. Hydroacylation of 1a with model phenyl boronic ester as molecular hydroacylation/Suzuki cross-coupling domino reaction
well as p-extended derivatives generated indanone derivatives (Scheme 3): oxidative addition to the coordinative IPr-Ni(0) complex
3a–d in moderate to high yields. Additionally, arylboronic A gives oxanickelacycle intermediate B, which is supported by
esters bearing substituted aryl rests could also undergo this earlier studies from Ogoshi.7d,e,8,9 Transmetallation with boronic
nickel catalyzed procedure smoothly. Fluoride-substituted aryl- acid neopentylglycol ester leads to C and subsequent reductive
boronic esters, including fluoro (2f), trifluoromethyl (2g), and elimination forms boryl-protected 1-indanol D. Hydrolysis affords
trifluoromethoxy derivatives (2h), were applicable in our trans- indenol E, which can be further oxidized to form the desired
formation and were converted into the corresponding products product 3.16 Alternatively, b-hydride elimination from B would lead
3f–h in good yields. Furthermore, substrates bearing methoxy to nickel hydride intermediate F.7d–f Direct transmetalation of
groups were tolerated without cleavage of the C–OMe bond.14 In F with boronic acid neopentylglycol ester or hydrolysis with sub-
addition, heterocyclic derivatives 2k–m were also compatible with sequent transmetalation would yield Ni intermediate H. Sub-
this methodology. Noteworthy, styryl boronic acid neopentyl sequent reductive elimination leads to the desired product 3. On
glycol ester provided the corresponding product 3n.
the other hand, acyl nickel(II) intermediate B0 is also feasible,
Encouraged by our satisfactory results, we next focused our hydroacylation of B0 leading to nickel hydride intermediate F which
attention on the domino reaction between various substituted can lead to the desired product 3 as described above.
o-allylbenzaldehydes and phenylboronic esters (Table 2). Hydro-
In summary, we have developed a nickel-catalyzed exo-
acylation of different functionalised benzaldehydes with phenyl- selective intramolecular hydroacylation/Suzuki cross-coupling
boronic esters 2a and 2j was investigated. 1-Napthaldehyde domino reaction. Various o-allylbenzaldehydes and a wide range
derivative provided the appropriate product 3o smoothly. As of phenylboronic acid neopentyl glycol esters are tolerated in
anticipated, both methyl and fluoro substituted benzaldehydes this process which affords indanone derivatives in a straight-
successfully provided the desired products 3p and 3q. Further- forward fashion. Notably, the substrate scope tolerates also
more, allylbenzaldehydes bearing an electron-donating methoxy heterocyclic and Csp2-boronic esters, providing the corresponding
group in the para- and meta-position, underwent this newly indanone products. Further synthetic applications are currently
developed methodology as well.
underway in our laboratories.
Scheme 3 Proposed mechanism for the intramolecular hydroacylation/Suzuki cross-coupling domino reaction.
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9 Y. Hayashi, Y. Hoshimoto, R. Kumar, M. Ohashi and S. Ogoshi,
Chem. Commun., 2016, 52, 6237.
Conflicts of interest
10 (a) L. F. Tietze, G. Brasche and K. M. Gericke, Transition Metal-
Catalyzed Domino Reactions, in Domino Reactions in Organic Synthesis,
Wiley-VCH, Weinheim, 2006, ch. 6, pp. 359–493; (b) Metal Catalyzed
Cascade Reactions, ed. T. J. J. Mu¨ller, Springer, Berlin, Top. Organomet.
Chem., 2006, vol. 19; (c) H. Pellissier, Curr. Org. Chem., 2016, 20,
234.
There are no conflicts to declare.
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