Palladium-Catalyzed Intramolecular Mizoroki-Heck-Type Reaction of Diarylmethyl Carbonates

Article abstract of DOI:10.1002/adsc.201901398

A palladium-catalyzed intramolecular Mizoroki-Heck-type reaction of diarylmethyl tert-butyl carbonates has been developed. The reaction proceeds under external base-free, neutral conditions to form the corresponding methyleneindanes in good yields only with liberation of CO₂ and tBuOH. The resulting exo-methylene moiety is reactive and thus a good synthetic handle for further manipulations. Additionally, the asymmetric synthesis is also possible through a Pd/chiral Mandyphos ligand-mediated kinetic resolution. To the best of our knowledge, this is the first successful example of catalytic enantioselective Mizoroki-Heck-type reaction of secondary benzyl electrophiles. (Figure presented.).

Full text of DOI:10.1002/adsc.201901398

Title: Palladium-Catalyzed Intramolecular Mizoroki-Heck-Type
Reaction of Diarylmethyl Carbonates
Authors: Akihiro Matsude, Koji Hirano, and Masahiro Miura
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10.1002/adsc.201901398
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Palladium-Catalyzed Intramolecular Mizoroki-Heck-Type
Reaction of Diarylmethyl Carbonates
Akihiro Matsude,a Koji Hirano,a,* and Masahiro Miuraa,*
a
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
Fax: (+81)-6-6879-7362; e-mail: k_hirano@chem.eng.osaka-u.ac.jp; miura@chem.eng.osaka-u.ac.jp
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
active starting substrates was necessary for obtaining
Abstract. A palladium-catalyzed intramolecular Mizoroki-
Heck-type reaction of diarylmethyl tert-butyl carbonates the targeted chiral products.
has been developed. The reaction proceeds under external
base-free, neutral conditions to form the corresponding
methyleneindane in good yields only with liberation of CO2
Thus, further
development of Mizoroki-Heck-type reaction of
secondary alkyl electrophiles, particularly, its
enantioselective version is highly appealing. Here, we
report a palladium-catalyzed intramolecular Mizoroki-
Heck-type reaction of diarylmethyl tert-butyl
carbonates. The reaction proceeds well under external
base-free conditions, and the corresponding
methyleneindanes are obtained in good yields.
Furthermore, the catalytic enantioselective synthesis is
possible through kinetic resolution using an optically
active Mandyphos ligand. To the best of our
knowledge, this is the first successful example of
and tBuOH.
The resulting exo-methylene moiety is
reactive and thus a good synthetic handle for further
manipulations. Additionally, the asymmetric synthesis is
also possible through a Pd/chiral Mandyphos ligand-
mediated kinetic resolution. To the best of our knowledge,
this is the first successful example of catalytic
enantioselective Mizoroki-Heck-type reaction of secondary
benzyl electrophiles.
Keywords: asymmetric catalysis; indanes; kinetic
resolution; Mizoroki-Heck reaction; palladium
catalytic
enantioselective
Mizoroki-Heck-type
reaction of secondary benzyl electrophiles.
During our recent studies on the palladium-
catalyzed benzylic substitution reactions of
diarylmethyl electrophiles,[5,6] we envisioned the
intramolecular Mizoroki-Heck-type reaction of
diarylmethyl tert-butyl carbonate 1a (Table 1). On the
basis of our previous results, we initially investigated
some bidentate bisphosphine ligands with relatively
large bite angles, in conjunction with the CpPd(3-
C3H5) catalyst and MeCN solvent, but the low
conversion was generally observed (entries 1–4). On
the other hand, the more common dppe and dppp
ligands with smaller bite angles showed good
reactivity (entries 5 and 6). Moreover, several
monodentate phosphine ligands, particularly,
Buchwald biarylphosphine ligands, were found to be
The transition-metal-catalyzed Mizoroki-Heck-type
reaction is now one of the indispensable carbon–
carbon bond forming reactions in modern organic
synthesis. In particular, the intramolecular variants
can construct unique cyclic frameworks, which are
frequently occurring in natural products and bioactive
molecules.[1] Under traditional conditions, Csp2-
hybridized organic halides are usually employed as the
carbon electrophiles, but recent progress allows Csp3-
hybridized alkyl electrophiles as well as less toxic and
more readily available phenol and alcohol derivatives
to be adopted in the Mizoroki-Heck-type reactions.[2]
Moreover, the asymmetric catalysis were also
developed by several research groups.[1b,d,2e,3] Despite
more
effective
(entries
7–12),
with
2-
dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl
1
the
aforementioned
certain
advances,
the
(XPhos) proving to be best (100% H NMR and 91%
isolated yield; entry 9). Additional solvent screening
were performed, but the reaction proceeded uniquely
in only MeCN solvent (entries 13–16).[7]
enantioselective Mizoroki-Heck-type reaction with
racemic secondary alkyl electrophiles still remains a
great challenge. In 2014, Jarvo reported a nickel-
catalyzed enantiospecific intramolecular Mizoroki-
Heck-type reaction of secondary benzyl ethers to from
the optically active methylenecyclopentanes.[4] This
reaction can successfully control the point chirality at
the benzylic position, which stems from the
electrophile. However, the strong external reductant,
MeMgI, was inevitable for the catalyst turnover.
Additionally, the tedious preparation of optically
The exo-methylene moiety in methyleneindane 2a
was reactive and thus readily elaborated (Scheme 1).
The hydrogenation under standard Pd/C catalysis
afforded the 1,2-disubstituted indane 3a with a 5:1
cis/trans ratio. The epoxidation with mCPBA was also
possible with the same diastereoselection, and the
corresponding epoxide 4a was obtained. Moreover,
1
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10.1002/adsc.201901398
Advanced Synthesis & Catalysis
the hydroboration/oxidation sequence provided the
oxidative addition of aryl-Cl to XPhos-ligated Pd0
species, the use of dppp instead of XPhos successfully
delivered the desired 2d in 74% yield. When the MeO
group was introduced on the naphthalene ring, the
reaction itself proceeded smoothly, but the
corresponding methyleneindane 2e was unstable for
silica gel column purification and thus isolated in the
saturated form 3e after the hydrogenation as shown in
Scheme 1. The 2-naphthalene substituent could be
replaced with 1-naphthalene (2f) and more condensed
phenanthrene (2g) and dibenzothiophene (2h). The
reaction was compatible with five-membered
heteroaromatic systems such as benzothiophene (2i)
and benzofuran (2j). Moreover, the monocyclic
thienyl-, biphenyl-, and even simple phenyl-
substituted substrates underwent the Mizoroki-Heck
reaction to produce 2k–2m in acceptable yields.
Additionally notable is the successful access to the
cyclopentanaphthalene scaffold (2n). Furthermore,
the internal olefin 1o was also viable to furnish the
benzylideneindane 2o with high E selectivity.
Although in some cases (2f, 2h, 2j, and 2m) the olefin
migration isomers 2’ were also detected, various
substituted indane derivatives were successfully
prepared under neutral conditions only with liberation
of CO2 and tBuOH.[9,10]
primary alcohol 5a with high cis selectivity.[8]
Table 1. Optimization Studies for Palladium-Catalyzed
Intramolecular
Mizoroki-Heck-Type
Reaction
of
Diarylmethyl tert-Butyl Carbonate 1a.[a]
Entry Ligand
Solvent
Yield [%][b]
1
2
3
4
5
6
7
8
rac-binap
dppf
DPEphos
xantphos
dppe
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
1,4-dioxane
DMF
0
13
0
24
74
79
35
57
dppp
PPh3
PPhCy2
XPhos
SPhos
RuPhos
Cy-JohnPhos
XPhos
XPhos
XPhos
XPhos
9
>99 (91)
10
11
12
13
14
15
16
96
91
96
0
28
9
DMSO
toluene
0
Conditions: 1a (0.20 mmol), CpPd(3-C3H5) (0.010
a)
mmol), ligand (0.010 mmol for bidentate ligands and 0.020
mmol for monodentate ligands), and solvent (1.5 mL), 60
b)
1
˚C, 16 h, N2. Estimated by H NMR using CH2Br2 as an
internal standard. Isolated yield in parentheses. Boc = tert-
butoxycarbonyl.
Scheme 1. Synthetic Elaborations of 2a.
We then examined the scope and limitation of the
present palladium catalysis with conditions of entry 9
in Table 1 (Scheme 2). The electron-donating MeO-
substituted substrates 1b and 1c were successfully
converted under the standard conditions, and the
corresponding methyleneindanes 2b and 2c were
isolated in 84% and 87% yields, respectively. In the
case of the Cl-substituted 1d, the reaction was
completely shut down. However, given the facile
Scheme 2. Palladium-Catalyzed Intramolecular Mizoroki-
Heck-Type Reaction of Various Diarylmethyl tert-Butyl
Carbonates 1. Standard conditions: 1 (0.20 mmol),
2
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10.1002/adsc.201901398
Advanced Synthesis & Catalysis
CpPd(3-C3H5) (0.010 mmol), XPhos (0.020 mmol), and
MeCN (1.5 mL), 60 ˚C, 16 h, N2. Isolated yields are shown.
The minor modifications from the standard conditions are in
parentheses. a) With 10 mol % of CpPd(3-C3H5) and dppp.
b) 1H NMR yield of 2e using CH2Br2 as an internal standard.
The isolated yield and cis/trans ratio of
Scheme 3. Enantioselective Mizoroki-Heck-Type Reaction
of Diarylmethyl tert-Butyl Carbonate 1. Conversion c = (e.e.
of 1)/(e.e. of 1 + e.e. of 2). Selectivity s = ln[(1 – c)(1 – e.e.
of 1)]/ln[(1 – c)(1 + e.e. of 1)]. Conditions: 1 (0.20 mmol),
CpPd(3-C3H5) (0.010 mmol), Mandyphos (0.010 mmol),
and 1,4-dioxane (1.5 mL), 60 ˚C, 16 h, N2. a) On a 1.0 mmol
b)
hydrogenated 3e are shown in
scale. In methyl tert-butyl ether (MTBE) instead of 1,4-
parentheses. c) The ratio of 2 and olefin
dioxane. Isolated as indane 3e in 36% yield (cis/trans = 7:1)
after the hydrogenation. 85:15 and 92:8 e.r. for cis- and
trans-isomers, respectively. c) The starting 1i was unstable
for chromatographic purification and analysis, and thus the
e.r. could not be determined.
migration isomer 2’ is shown in
parentheses.
See the Supporting
Information for details.
The prevalence of optically active indane structures
in biologically active compounds and natural
products[11] prompted us to develop the catalytic
enantioselective Mizoroki-Heck-type reaction of 1a.
After the extensive screening of various chiral
phosphine ligands, we were pleased to find that the
combination of CpPd(3-C3H5) and (Rp,R’p)-(S)-
Mandyphos ligand in 1,4-dioxane successfully
induced the enantioselectivity (Scheme 3): the
enantioenriched (S)-2a was obtained in 42% yield with
93:7 enantiomeric ratio (e.r.). The reaction occurred
in a kinetic resolution manner, and thus the unreactive
starting substrate (S)-1a was recovered also in an
enantioenriched form (43%, 94:6 e.r., c = 51%, s =
35).[12] Additional examples with the (Sp,S’p)-(R)-
Mandyphos ligand were also illustrated. The racemic
1b–e were catalytically converted to the optically
active methyleneindanes (R)-2b–e with 85:15–94:6 e.r.
Again, the kinetic resolution was observed, and the
remaining substrates were enantiomerically enriched
(c = 45–49%, s = 12–37). On the other hand, the
benzothiophene substrate 1i decreased the reactivity
and enantioselectivity ((S)-2i). The reaction could also
be performed on a 1.0 mmol scale, thus indicating the
good reproducibility of the asymmetric catalysis ((R)-
2a).
To get insight into the stereochemical course, we
implemented some control experiments with the
independently prepared (S)-1a (97:3 e.r.; Scheme 4).
The reaction under non-enantioselective conditions
with XPhos afforded (R)-2a with a drop of e.r. but with
inversion of configuration. Subsequent investigations
under asymmetric catalysis showed the significant
match/mismatch phenomena: the Pd/(Rp,R’p)-(S)-
Mandyphos catalyst resulted in no conversion,
whereas the optically active (R)-2a was readily formed
with 98:2 e.r. under Pd/(Sp,S’p)/(R)-Mandyphos
catalysis. This outcome is consistent with the kinetic
resolution mechanism.
Scheme 4. Control Experiments with (S)-1a.
On the basis of the above findings and literature
information, we attempted to propose that the
mechanism of the reaction of 1a is as follows (Scheme
5). The initial stereoinvertive SN2-type oxidative
addition[13] of Pd0Ln [L = (Rp,R’p)-(S)-Mandyphos] to
(R)-1a and (S)-1a can form the corresponding -
benzylpalladium[14] intermediates
6
and 6’,
respectively. However, in this step the kinetic
resolution occurs to generate one diastereomer 6
selectively. Subsequent olefin coordination and
insertion provide the alkylpalladium species (6 to 7 to
8). The observed (S)-2a then follows from -H
elimination. The catalytic cycle is completed with
concomitant elimination of CO2 and tBuOH. Given
the results in Scheme 3, the conceivable
stereochemical erosion through the equilibrium[15]
3
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10.1002/adsc.201901398
Advanced Synthesis & Catalysis
Scheme 5. Plausible reaction mechanism of 1a with (Rp,R’p)-(S)-Mandyphos ligand.
Research) to M.M. We thank Dr. Yuji Nishii (Osaka University)
for his assistance with X-ray analysis.
between 6 and 6’ is almost negligible under the
enantioselective conditions but somewhat competitive
under nonenantioselective conditions using the XPhos
ligand (Scheme 4).
References
In conclusion, we have developed a palladium-
catalyzed intramolecular Mizoroki-Heck-type reaction
of diarylmethyl carbonates to form the corresponding
methyleneindanes in good yields under external base-
free, neutral conditions. Additionally, the asymmetric
synthesis is possible through the kinetic resolution
with the chiral Mandyphos ligand. To the best of our
knowledge, this is the first successful example of
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Experimental Section
CpPd(3-C3H5) (2.1 mg, 0.010 mmol) and (Rp,R’p)-(S)-
Mandyphos (8.2 mg, 0.010 mmol) were placed in a 4 mL
screw cap vial in a glovebox filled with nitrogen. 1,4-
Dioxane (0.5 mL) was added to the vial, and suspension was
stirred for 10 min. The mixture was transferred to an another
4 mL screw cap vial containing (2-allylphenyl)(naphthalen-
2-yl)methyl tert-butyl carbonate (1a; 74.9 mg, 0.20 mmol)
with additional 1,4-dioxane (1.0 mL). The vial was sealed
with a cap and taken out of the glovebox. The suspension
was stirred for 16 h at 60 °C. The resulting mixture was
filtered through a short pad of activated alumina and sodium
sulfate. Concentration in vacuo and subsequent purification
by column chromatography on neutral silica gel with
hexane/ethyl acetate (40/1 to 20/1 v/v) as an eluent gave (S)-
2-(2-methylene-2,3-dihydro-1H-inden-1-yl)naphthalene
[(S)-2a; 22 mg, 8.4 × 10-2 mmol, 93:7 e.r.)] in 42% yield:
enantiomeric ratio was determined by HPLC analysis in
comparison with authentic racemic sample (CHIRALPAK
AD-H column, n-hexane/isopropyl alcohol = 99.7/0.3, 0.5
mL/min, major isomer: tR = 11.8 min, minor isomer: tR =
12.7 min, UV detection at 275.0 nm, 30 oC). The unreacted
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determined by HPLC analysis in comparison with authentic
racemic sample (CHIRALCEL OJ-H column, n-
hexane/isopropyl alcohol = 97/3, 0.5 mL/min, major isomer:
tR = 13.6 min, minor isomer: tR = 10.1 min, UV detection at
256.0 nm).
Acknowledgements
This work was supported by JSPS KAKENHI Grant Nos.
18K19078 (Grant-in-Aid for Challenging Research (Exploratory))
to K.H. and JP 17H06092 (Grant-in-Aid for Specially Promoted
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10.1002/adsc.201901398
Advanced Synthesis & Catalysis
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otherwise identical conditions.
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competitive -H elimination. See the Supporting
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5
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Advanced Synthesis & Catalysis
COMMUNICATION
Palladium-Catalyzed Intramolecular Mizoroki-
Heck-Type Reaction of Diarylmethyl Carbonates
Adv. Synth. Catal. Year, Volume, Page – Page
Akihiro Matsude, Koji Hirano,* and Masahiro
Miura*
6
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