Ferrocenylindium Reagents in Palladium-Catalyzed Cross-Coupling Reactions: Asymmetric Synthesis of Planar Chiral 2-Aryl Oxazolyl and Sulfinyl Ferrocenes

Article abstract of DOI:10.1002/adsc.201601397

The preparation of ferrocenylindium species and palladium-catalyzed cross-coupling reactions for the synthesis of monosubstituted and planar chiral 1,2-disubstituted ferrocenes is described. Triferrocenylindium reagents (Fc₃In) are efficiently

Full text of DOI:10.1002/adsc.201601397

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DOI: 10.1002/adsc.201601397
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Ferrocenylindium Reagents in Palladium-Catalyzed
Cross-Coupling Reactions: Asymmetric Synthesis of Planar Chiral
2-Aryl Oxazolyl and Sulfinyl Ferrocenes
a
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Mauro Mato, Cristina Perez-Caaveiro, Luis A. Sarandeses, and
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Jose Perez Sestelo *
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Centro de Investigaciones Cientıficas Avanzadas (CICA) and Departamento de Quımica Fundamental, Universidade da
˜
Coruna, Spain
Fax: (+34)-981-167-065; e-mail: sestelo@udc.es
Received: December 21, 2016; Revised: January 30, 2017; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201601397
netic properties.[6] In addition, the planar chirality of
1,2-disubstituted ferrocenes makes them important
Abstract: The preparation of ferrocenylindium spe-
cies and palladium-catalyzed cross-coupling reac-
ligands in asymmetric catalysis. In this field, chiral
tions for the synthesis of monosubstituted and
ferrocenylphosphines such as ppfa (N,N-dimethyl-1-
planar chiral 1,2-disubstituted ferrocenes is de-
[2-(diphenylphosphino)ferrocenyl]ethyl-amine),
2-
scribed. Triferrocenylindium reagents (Fc3In) are
efficiently prepared in a one-pot procedure from
ferrocenes by lithiation and transmetallation to
indium using InCl3. The palladium-catalyzed cross-
coupling reactions of Fc3In (40 mol%) with a
variety of organic electrophiles (aryl, heteroaryl,
benzyl, alkenyl and acyl halides) in THF at 808C
overnight provided a wide variety of monosubsti-
tuted ferrocenes in good to excellent yields. This
methodology allowed the stereoselective synthesis
of planar chiral 2-aryl-1-oxazolylferrocenes and 2-
aryl-1-sulfinylferrocenes, which are of interest in
asymmetric catalysis.
aryl-monophosphine ferrocenes (aryl-MOPF), or
ferrocenyl phosphino-oxazolines (Fc-PHOX) are priv-
ileged ferrocene ligands (Figure 1).[2a,7] Therefore, the
development of efficient methods for the synthesis of
functionalized and enantiomerically pure ferrocenes is
of great importance.[2,8]
Keywords: Asymmetric synthesis; Cross-coupling;
Ferrocene ligands; Indium; Palladium
Figure 1. Privileged ferrocene ligands in asymmetric cataly-
sis.
44 Ferrocene and derivatives are compounds of great
45 interest in different areas of chemistry due to their
Metal-catalyzed cross-coupling reactions are
46 fascinating structural and electronic properties.[1] The amongst the most powerful tools available for the
47 applications of ferrocene derivatives are constantly construction of new carbon-carbon bonds.[9] Although
48 increasing, especially in organic synthesis,[2] materials this methodology has already been applied to the
49 science[3] and medicinal chemistry.[4] Ferrocene, for its synthesis of ferrocenes,[8e–g,10] it often suffers from
50 aromatic character, can be considered a bioisotere of limitations such as low atom efficiency, the need for
51 a phenyl ring, and established drugs such as anticancer harsh reaction conditions or the use of highly toxic
52 taxol, or antimalarial artemisinin, have been modified compounds. Over the last two decades, triorganoin-
53 by using ferrocene as a substituent in their core dium compounds (R3In), which can be easily prepared
54 structure.[5] On the other hand, the inherent electro- from the corresponding organolithium or organic
55 chemical properties of the ferrocene unit have led to halide, have emerged as alternative reagents in metal-
56 its introduction in complex structures to provide new catalyzed reactions.[11] The palladium-catalyzed cross-
57 molecules with novel nonlinear optical or ferromag- coupling reaction using R3In, which was discovered by
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our group,[12] is the most useful reaction of these should be noted that the coupling reaction is not
reagents and its utility in organic synthesis is increas- efficient if indium is not used. Interestingly, the
ing steadily.[13] Besides their high atom efficiency due reaction can be monitored by observing the colour of
to the transfer of all three organic groups from indium the reaction mixture, which shows the different steps
to the electrophile, R3In reagents show excellent in this chemical transformation.[15] The reaction can be
selectivity, high versatility and, in general, low toxicity. performed using palladium(II) complexes such as
In this communication we describe the novel prepara- Pd(dppf)Cl2 to afford the coupling product in similar
tion of triferrocenylindium reagents and their applica- yield. The reaction was easily scaled up to gram-scale
tion in palladium-catalyzed cross-coupling reactions obtaining a similar yield (85%).
10 for the synthesis of monosubstituted and planar chiral
11 1,2-disubstituted ferrocenes.
To exploit the scope of this protocol, the palla-
dium-catalyzed coupling reaction using Fc3In was
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Our investigation started with the one-pot proce- evaluated with a variety of organic halides (Table 1).
13 dure involving lithiation of ferrocene, transmetallation During this research we found that the metallation/
14 to indium and palladium-catalyzed coupling. It was transmetallation/coupling works efficiently with aryl
15 found that direct lithiation of ferrocene using standard halides bearing electron-rich substituents such as 4-
16 reaction conditions (tBuLi/tBuOK at À788C in bromotoluene, 2-bromoanisole and 4-iodoanisole to
17 THF),[14] followed by addition of anhydrous InCl3 give the corresponding phenyl substituted ferrocenes
18 (40 mol%) and coupling with bromobenzene 1b–d in high yields (70–88%). Analogously, the cross-
19 (100 mol%), using Pd(PPh3)4 (5 mol%) as catalyst in coupling using electron-deficient arenes such as 4-
20 THF at 808C overnight, gave phenylferrocene (1a) in trifluoromethyl bromobenzene and 4-bromoacetophe-
21 90% yield (Table 1). This result supports the forma- none also afforded the phenylferrocenes 1e and 1f in
22 tion of the Fc3In intermediate and the efficient trans- 85% and 65% yields, respectively. It is remarkable
23 fer of the three ferrocene units attached to indium. It that the coupling is not sensitive to the nature of the
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substituent on the phenyl halide and all of the
reactions proceeded efficiently at 808C overnight. It
was observed, however, that in some examples the
highest yield was obtained on using Pd(dppf)Cl2 as the
catalyst.
Table 1. Pd-catalyzed cross-coupling of Fc3In with organic
electrophiles.
The reaction of Fc3In with bulky electrophiles such
as 9-bromoanthracene or 1-bromonaphthalene, which
usually require specific reaction conditions (high
temperature, excess of the organometallic or
additives),[16] also gave the corresponding 9-anthranyl-
ferrocene (1g) and 1-naphthylferrocene (1h) at 808C
overnight in high yields (91% and 70%, respectively).
Analogously, the coupling with heteroaryl halides
allowed the synthesis of interesting substituted ferro-
cenes bearing nitrogen donor atoms, e.g., 3-pyridylfer-
rocene (1j), 2-pyridylferrocene (1k), 1-isoquinolinyl-
ferrocene (1i) and 2,6-dichloro-4-pyrimidylferrocene
(1l).[17] This study was also extended to organic
electrophiles other than aryl halides and these allow
further chemical transformations that are useful for
the synthesis of new ferrocene derivatives. The cross-
coupling of Fc3In with b-bromostyrene (E:Z 80:20)
allowed the introduction of the alkene functionality
(1m) and the reaction with benzyl bromide and
benzoyl chloride gave the corresponding monosubsti-
tuted ferrocenes 1n and 1o in good yields (70—80%).
It is noteworthy that all reactions take place with only
40 mol% of Fc3In in THF at 808C to afford the
coupling product in good to excellent yields.
The synthetic utility of ferrocenylindium reagents
in palladium-catalyzed cross-coupling reactions was
also tested for the stereoselective synthesis of planar
chiral 1,2-disubstituted ferrocenes. Ferrocene deriva-
tives that contain a chiral directing group such as an
[b]
[a] In parenthesis, isolated yield at gram-scale. Pd(dppf)Cl2
[c]
(5 mol%) used as the catalyst. E:Z 80:20.
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oxazoline,[18] or a sulfoxide,[19] can be ortho-lithiated chromatography. The analogous protocol using 2-
diastereoselectively under the appropriate conditions. bromopyridine afforded the chiral (RP)-2-pyridyl-1-
In this study we envisioned that the resulting organo- oxazolylferrocene 3d in 70% yield (6:1 dr by 1H
lithium species could be transformed into the corre- NMR). Apart from the existing synthetic methods for
sponding triferrocenylindium reagents and used in the preparation of ferrocenyloxazolines,[7a] these cross-
palladium-catalyzed cross-coupling reactions.
coupling reactions are the first examples in which
We began by exploring the lithiation/transmetalla- oxazolylferrocenyl organometallics have been used for
tion/coupling protocol using the achiral ferrocenyl the enantioselective synthesis of 2-pyridyl-1-oxazolyl-
oxazoline 2a. As described in the literature, lithiation ferrocene ligands with planar and central chirality.
[20]
10 of 2a (100 mol%) with nBuLi in THF at À788C
Our next objective was the enantioselective syn-
11 followed by addition of InCl3 (40 mol%) and coupling thesis of 2-aryl-1-sulfinylferrocenes using an enantio-
12 with 2-bromoanisole (100 mol%) in the presence of pure ferrocenyl sulfoxide. The sulfoxide functionality
13 Pd(dppf)Cl2 (5 mol%) in THF at 808C gave the 2-aryl- can be used as a chiral ortho metallating group with
14 1-oxazolylferrocene 3a in 72% yield (Table 2). Analo- high diastereoselectivity and its subsequent conversion
15 gously, the reaction using 1-bromonaphthalene allows the stereoselective synthesis of 1,2-disusbtituted
16 afforded the 2-(1-naphthyl)-1-oxazolylferrocene 3b in ferrocenes.[10d,21] Accordingly, lithiation of enantiopure
17 77% yield. To the best of our knowledge, these results p-tolyl ferrocenyl sulfoxide (S)-4 using LDA in THF
18 represent the first examples of palladium-catalyzed at À788C,[14] followed by addition of InCl3 solution
19 cross-coupling reactions involving an organometallic (40 mol%) gave the tri(2-sulfinylferrocenyl)indium
20 ferrocenyloxazoline.
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intermediate (Scheme 1). Palladium-catalyzed cross-
coupling with 1-bromonaphthalene using Pd(dppf)Cl2
(5 mol%) afforded the planar chiral (S,SP)-2-(1-
naphthyl)-1-sulfinylferrocene 5a in 74% yield as a
single enantiomer (>99:1 by HPLC). Therefore, the
lithiation step takes place with high diastereoselectiv-
ity and both the transmetallation and coupling steps
proceed without affecting the stereoselectivity. In a
similar manner, the procedure carried out with 2-
bromonaphthalene and 4-trifluoromethylbromoben-
zene as organic electrophiles gave the enantiomeri-
cally rich (S,SP)-2-aryl-1-sulfinyl ferrocenes 5b and 5c
with high diastereomeric excess (de >98%) in 60%
and 65% yield, respectively.
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Table 2. Synthesis of 2-aryl-1-oxazolylferrocenes.
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These encouraging results led us to study the
42 stereoselective synthesis of 2-aryl-1-oxazolylferro-
43 cenes. For this purpose, substrates bearing donor
44 atoms such as pyridines were selected as electrophiles.
45 Under the previously developed reaction conditions,
46 lithiation of the enantiomerically pure ferrocenyl
47 oxazoline 2b with nBuLi, transmetallation with in-
48 dium and palladium-catalyzed cross-coupling with 3-
49 bromopyridine using Pd(dppf)Cl2 (5 mol%) in THF
50 under reflux gave (RP)-2-(3-pyridyl)-1-oxazolylferro-
Scheme 1. Synthesis of (S,SP)-2-aryl-1-sulfinylferrocenes.
51 cene 3c in 68% yield with an 8:1 diastereomeric ratio,
Finally, and taking advantage of the versatility of
1
52 as determined by H NMR spectroscopy (Table 2). the sulfoxide group, the enantiomerically rich (S,SP)-2-
53 This dr value is equal or slightly higher than that aryl-1-sulfinylferrocenes 5a–c were transformed into
54 previously reported for the lithiation step, which the corresponding 2-aryl-1-monophosphine ferrocenes.
55 indicates that the transmetallation-coupling steps take Following a reported procedure,[19] the sulfoxide group
56 place without loss of diastereoselectivity. The two was converted into a diphenylphosphine group to give
57 diastereoisomers were separated by flash column the planar-chiral phosphines (SP)-6a–c in good yields
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phere, equipped with a Teflon-coated magnetic stirring bar,
was charged with ferrocene (1.0 g, 5.375 mmol, 1.0 equiv.).
The ferrocene was dissolved in dry THF (40 mL, 0.134 M for
ferrocene) and tBuOK solution (0.65 mL, 1.0 M in THF,
0.12 equiv.) was added by syringe. The mixture was cooled to
À788C. The resulting yellow solution was treated with tBuLi
solution (6.3 mL, 1.64 M in pentane, 2.0 equiv.) over 15
minutes by syringe and the resulting orange suspension was
stirred at À788C for 90 min. Then, InCl3 solution (4.8 mL,
0.45 M in THF, 0.4 equiv.) was added dropwise and the
reaction mixture was allowed to warm up to 08C and stirred
for 1 h to give triferrocenylindium (1.79 mmol, 0.034 M in
THF) as an orange homogeneous solution, which was
immediately used for the cross-coupling step.
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(Table 3). The enantiomeric purity of phosphines 6a–c
was established based on the enantiomeric excess of
the chiral sulfoxides 5a–c since the transformation is
stereospecific.[19b–d,21] It is worth noting that the (SP)-2-
(1- naphthyl)-diphenylphosphine ferrocene 6a exhibits
high catalytic activity in the hydrosilylation of styr-
ene.[21b] The utility of the novel chiral phosphines 6b–c
in asymmetric catalysis is still unknown.
Table 3. Synthesis of planar chiral (SP)-2-aryl-1-diphenyl-
phosphine ferrocenes.
General procedure for the palladium-catalyzed cross-cou-
pling reaction. A flame-dried Schlenk flask under an argon
atmosphere, equipped with a Teflon-coated magnetic stirring
bar, was charged with the organic halide (1.0 equiv.) and
Pd(PPh3)4 (5 mol%) or Pd(dppf)Cl2 (5 mol%). The mixture
was dissolved in dry THF (ca. 0.3 M) and freshly prepared
Fc3In solution (0.034 M in THF, 0.4 equiv.) was added
dropwise by syringe or cannula. The mixture was heated at
808C overnight (16–18 h). The reaction was monitored by
TLC and, after completion, quenched by the addition of a
few drops of methanol and then tap water. The mixture was
extracted with Et2O or EtOAc three times and the combined
organic phases were washed with brine and dried over
anhydrous MgSO4. The crude product was obtained by
removal of the solvent under reduced pressure and it was
purified by flash column chromatography (silica gel) to give
the corresponding functionalized ferrocenes (65–95% yield).
In summary, a practical and efficient procedure for
29 the synthesis of monosubstituted and planar chiral 1,2-
30 disubstituted ferrocenes by palladium-catalyzed cross-
31 coupling reactions using triferrocenlylindium reagents
32 has been developed. Fc3In reagents can be efficiently
33 prepared from ferrocene and derivatives by lithiation
34 and transmetallation with indium(III). Fc3In reagents
35 (40 mol%) react with an array of organic electrophiles
36 to provide an interesting range of monosubstituted
37 ferrocenes in good yields under mild reaction con-
38 ditions. The diastereoselective lithiation, transmetalla-
39 tion to indium and cross-coupling of chiral (S)-
40 ferrocenyloxazolines led to the synthesis of planar
41 chiral (RP)-2-aryl-1-oxazolylferrocenes. Analogously,
42 the coupling reaction in which tri(2-sulfinylferrocenyl)
43 indium was used led to (S,SP)-2-aryl-1-sulfinylferro-
44 cenes in good yields and with high diastereoselectivity.
45 These compounds were efficiently converted into the
46 corresponding N,P-2-aryl-1-diphenylphosphine ferro-
47 cenes (MOPF), which are of interest in asymmetric
48 catalysis. Further applications of this synthetic method
49 for novel planar chiral ferrocenes are underway.
50
Acknowledgements
We gratefully acknowledge the Spanish Ministerio de Econo-
´
mıa y Competividad (CTQ2015-68369-P), Xunta de Galicia
(GRC2014/042) and EDRF funds for financial support.
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