A phosphine-free iron complex-catalyzed synthesis of cycloalkanes: Via the borrowing hydrogen strategy

Article abstract of DOI:10.1039/d0cc05840h

Herein we report a diaminocyclopentadienone iron tricarbonyl complex catalyzed synthesis of substituted cyclopentane, cyclohexane and cycloheptane compounds using the borrowing hydrogen strategy in the presence of various substituted primary and secondary 1,n diols as alkylating reagents. Deuterium labeling experiments confirm that the diols were the hydride source in this cascade process. This journal is

Full text of DOI:10.1039/d0cc05840h

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DOI: 10.1039/D0CC05840H
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A
Phosphine-Free Iron Complex-Catalyzed Synthesis of
Cycloalkanes via the Borrowing Hydrogen Strategy
Léo Bettoni, Sylvain Gaillard and Jean-Luc Renaud*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Herein we report a diaminocyclopentadienone iron tricarbonyl functionalized building blocks. This protocol has been well
complex catalyzed the synthesis of substituted cyclopentane, explored for the -mono-alkylation of ketones with primary
cyclohexane and cycloheptane compounds using the borrowing alcohols8-9 and, more recently, with secondary alcohols.10-11 Few
hydrogen strategy in the presence of various substituted primary synthesis of -dialkylated ketones have been also recently
and secondary 1,n diols as alkylating reagents. Deuterium labeling reported via the alkylation of substituted methylene ketones,
experiments confirm that the diols were the hydride source in this consecutive double alkylation of methyl ketones or tandem
cascade process.
three-component alkylation.12-13 The inter/intra-molecular
version of the double alkylation methodology with 1,n-diols
would lead to the corresponding cycloalkanes. Donohoe and
coworkers reported the first inter-/intramolecular double
alkylation catalyzed by an iridium complex in the presence of
pentamethylphenyl (Ph*) acetophenone, various primary or
secondary diols compounds and an excess of base (4 equiv.) at
115 °C (Scheme 1).14 The success of this process relied on the
introduction of the Ph* substituent which generated a twist out
of the conjugation with the carbonyl function (and
consequently modified the nucleophilic character of the
ketone), prevented the self-dimerization in basic conditions. A
complex mixture of compounds was obtained in the absence of
Cycloalkanes constitute a class of compounds omnipresent in
organic chemistry. Among these compounds, cyclohexane
derivatives are encountered in plethora of natural products,
pharmaceuticals or materials.1 Several strategies have been
described in the literature for the preparation of substituted
cyclohexanes. As examples, the Diel-Alder reaction,2 the
hydrogenation of aryl derivatives,3 or the ring closing
metathesis4 can be cited. However, these approaches involve
multistep procedures and functionalized precursors.
A
complementary method could be the double alkylation of a
methyl ketone with a double electrophile.5 However, such
strategy implies the formation of an enolate under cryogenic
conditions, the use of toxic halides or pseudo-halides
compounds and the generation of waste.6-7
The -alkylation of ketones via the borrowing hydrogen or
hydrogen autotransfer methodology is a growing and dynamic
domain of research and constitutes a greener and safer
alternative to the well-known enolate chemistry.8-9 The
alkylating agent is an alcohol, a cheap, ubiquitous and easily
accessible starting material. The process, catalyzed by a metal-
based complex including Earth-abundant ones, is initiated by
the abstraction of a hydrogen atom from the alcohol to form a
carbonyl derivative. After an aldol/dehydration sequence, the
complex “returns” the hydrogen atom to reduce the in-situ
generated activated alkene, leading to the synthesis of
a
starting ortho-disubstituted ketone. Leitner and Maji
proposed almost simultaneously to replace the iridium complex
by a more abundant metal-based one. The use of pincer type
manganese complexes at 140-150 °C allowed the formation of
the cycloalkyl pentamethylphenyl ketones in 31-98% yields
(Scheme 1).15-16 Both groups extended also the concept of this
cyclization by using secondary benzylic alcohols in the presence
of primary diols (Scheme 1).15-16 The corresponding cycloalkyl
alcohols were isolated in moderate to good yields (40-83%,
Scheme 1). These results pointed out again the crucial role of
the Ph* substituent to prevent overreduction of the resulting
cycloalkyl ketones.
Normandie Univ, LCMT, ENSICAEN, UNICAEN, CNRS, 6 boulevard du Maréchal
Juin, 14000 Caen, France.
† Footnotes relating to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
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Journal Name
O
O
[Cp*IrCl2]2 (2 mol%)
Table 1. Optimization of the reaction conditions.a
OH
View Article Online
Donohoe, 2018
HO
+
Ph*
Ph*
n
KOH (4 equiv.), PhMe (4 M)
115 °C, 24 h
n
DOI: 10.1039/D0CC05840H
O
O
n = 1,2,3
n = 1,2,3
Fe
(2 mol%), Me3NO (4 mol%)
+
HO
OH
base, solvent, T °C, time
OH
OH
2a
Ph
Ph
Ph*
Ph
n
Mn-1 (2 mol%)
OH
Leitner, 2019
or
+
HO
n = 1,2,3
n
KOtBu (4 equiv.), PhMe (0.25 M)
150 °C, 24 h
entry
Fe
base
(equiv.)
solvent
temp.
(°C)
conv.b
(%)
O
O
n = 1,2,3
Ph*
n
1
2
3
4
5
Fe1
Fe1
Fe1
Fe1
Fe1
Fe1
Fe1
Fe1
Fe1
Fe2
Fe3
Fe4
NaOtBu (2)
NaOtBu (2)
NaOtBu (2)
NaOtBu (2)
NaOtBu (4)
K3PO4 (4)
K2CO3 (4)
NaOH (4)
NaOH (4)
NaOH (4)
NaOH (4)
NaOH (4)
toluene (1 M)
toluene (1 M)
toluene (3 M)
toluene (5 M)
toluene (5 M)
toluene (5 M)
toluene (5 M)
toluene (5 M)
toluene (5 M)
toluene (5 M)
toluene (5 M)
toluene (5 M)
110
130
130
130
130
130
130
130
140
130
130
130
-
19
20
26
36
18
10
84 (79)e
82
OH
OH
Ph
n
Mn-2 (4 mol%)
OH
or
O
+
HO
Maji, 2020
n = 1,2,3
n
KOtBu (2 equiv.), tAmOH (1 M)
140 °C, 36 h
O
n = 1,2,3
Ph*
Ph*
6
7
n
8c,d
9c,d
10c,d
11c,d
12c,d
Br
CO
Me
H
N
N
PiPr2
N
Ph* =
Mn
Mn
Br
61
19
4
S
CO
P
CO
OC
CO
iPr
2
Mn-1
Mn-2
a General Conditions: ketone (0.5 mmol), diol (1 mmol), Fe (2 mol%), Me3NO (4 mol
%), base (4 equiv.), toluene (0.1 mL) for 24 h. b Conversions were determined by
1H-NMR analysis of the crude mixture. c Reaction performed without Me3NO. d for
40 h. e isolated yield in bracket.
Scheme 1. Previous syntheses of cycloalkanes via the borrowing hydrogen strategy
We and Morrill have recently highlighted the versatility of the
diaminocyclopentadienone iron tricarbonyl complex Fe1 as pre-
catalyst for the formation of C-C bonds in the alkylation of
A screening of temperature revealed that a temperature
threshold of 130 °C was necessary to convert the methyl ketone
into the cycloalkyl pentamethylphenyl ketone 2a in the
presence of 2 mol% of iron complex Fe1 (entries 1-2, Table 1).
No improvement was noticed at higher temperature (entries 8-
9, Table 1). An excess of diols was also required in this double
alkylation (entries 1-2, Table S1). The higher the concentration,
the better the conversion (entries 2-5, Table 1). One of the key
parameters was the base. Indeed, NaOH provided the product
with the highest conversion (84%) within 40 h (entry 8, Table 1),
when other bases such as K2CO3, K3PO4 or NaOtBu furnished the
alkylated ketone 2a in up to 36% conversion (entries 5-7, Table
1). The iron complex Fe2, an analog of Fe1, catalyzed also the
alkylation and provided the cyclohexyl aryl ketone 2a but in a
somewhat lower conversion (entries 8 and 10, Table 1). The
other cyclopentadienone iron complexes Fe3 and Fe4 were
almost inefficient in this process (entries 11-12, Table 1) and no
conversion was observed in the absence of iron complex (entry
18, Table S1). When the pentamethylphenyl ketone was
replaced by acetophenone, a complex mixture of compounds
13b, 17a, 18a-b
18a
ketones,10d,
indoles,17b,
oxindoles18a,c and
alcohols,17c, 18d and the methylation and ethylation of amines via
the hydrogen auto-transfer technology.18a, 19 Based on these
results and previous works by Donohoe and Maji, the synthesis
of cycloalkanes (from cyclopentanes to cycloheptanes) was
planned via the dialkylation of a ketone with a variety of
substituted primary and secondary diols in the presence of the
iron complex Fe1 (Scheme 2).
Scheme 2. Outline of the Fe-catalyzed synthesis of cycloalkanes
As model substrates for the optimization of the reaction
conditions, we initially used 1,5-pentan-diol and
pentamethylphenyl (Ph*) acetophenone (Table 1 and S1). The
latter was chosen as it was the key for the success of the
alkylation of ketones with secondary alcohols,13b and because
the alkylated ketone can be further transformed and
functionalized into esters, amides or other aromatic ketones, as
elegantly demonstrated by Donohoe.10a-b, 14
The iron complexes Fe1-4 were activated either by addition of
Me3NO20 or by addition of hydroxide (Hieber’s method).21
thorough screening of the reaction conditions were
accomplished and showed in Table 1 and S1.
1
was observed by H-NMR analysis, highlighting the key role of
the Ph* substituent in this cascade reaction. In summary the
optimized conditions were as follows: 0.5 mmol of pentamethyl
phenyl ketone underwent a double alkylation in the presence of
2 equiv. of diol, 2 mol% of complex Fe1 and 4 equiv. of NaOH at
130 °C in toluene (5 M) to provide the ketone 2a in 79% yield.
Having established the optimized reaction conditions, the scope
of this new iron catalysis was explored.
To ensure the synthetic applicability of this methodology, a
gram scale alkylation of the pentamethylphenyl ketone with
1,5-pentan-diol was carried out and 2a was isolated in 78%
yield.
A
2 | J. Name., 2012, 00, 1-3
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O
O
cyclopentanes 2q and 2r were obtained as a single trans-
View Article Online
R
Fe1 (2 mol%), NaOH (4 equiv.)
diastereomer (d.r. = >95:5) while tDhOeI: 110,.310,43-9/Da0nCdC0158,24,05H-
trisubstituted cyclopentanes 2s and 2t were isolated as a
mixture of diastereomers (70:30 in favor of the meso-
diastereomer and 70:17:13, respectively, Scheme 4). A geminal
dimethyl group in diol did not hamper the reactivity and
afforded the alkylated product 2u in 55% yield. Pleasingly, the
reaction between the Ph* ketone and 1,6-hexane diol led to
cycloheptane 2v in 73% isolated yield. As noticed in previous
works, substituted cyclopheptanes were prepared in good
yields but with a moderate control of the diastereoselectivity
(Scheme 4). Disubstituted cycloheptanes 2w and 2x were
synthesized in 67 and 64% yield, respectively, as almost a 1:1
mixture of diastereomers (Scheme 4).
R
HO
OH
O
+
toluene (5 M), 130 °C, 40 h
O
O
O
2d, 76%
2c, 77%
85:15 d.r.
2a, 79%
2b, 54%
O
O
O
2e, 74%
2g, 72%
2f, 78%
>95:5 d.r.
O
O
O
O
O
OMe
F
2h, 76%
>95:5 d.r.
2j, 78%
>95:5 d.r.
2i, 80%
>95:5 d.r.
O
O
O
Fe1 (2 mol %), NaOH (4 equiv.)
O
OH
HO
+
n
H
n
toluene (5 M), 130 °C, 40 h
n = 1,3
n = 1,3
2k, 71%
>95:5 d.r.
O
O
2l, 69%
>95:5 d.r.
O
O
O
O
Ph
2q, 48 %
>95:5 d.r.
O
2r, 65 %
>95:5 d.r.
O
2p, 56 %
O
2n, 76%
90:10 d.r.
2o, 77%
>95:5 d.r.
2m, 71%
Scheme 3. Scope of the iron-catalyzed synthesis of cyclohexanes.
2s, 67 %
70:30 d.r.
2u, 55 %
2t, 46 %
70:17:13 d.r.
A variety of differently substituted 1,5-diols were engaged in
the optimized conditions for the synthesis of functionalized
cyclohexyl derivatives (Scheme 3). Electron-donating (alkyl,
methoxy, acetal) and electron-withdrawing groups (fluoride) on
the aryl ring were tolerated in these conditions. Ketones 2g-k,
2m and 2o were isolated in good yields (71-80%, Scheme 3).
Alkyl substituent can also be introduced on the diols and the
corresponding ketones 2a-f, 2l and 2n were obtained in
moderate to good yields (54-79%, Scheme 3). Starting from 3-
substituted 1,5-pentan-diols, only the trans-1,4-disubstituted
cyclohexanes 2g-k were isolated (Scheme 3). The control of the
diastereoselectivity was lower when 2-methyl-1,5-pentan-diol
was used as electrophile. The corresponding ketone 2c was
O
O
O
2v, 73 %
2w, 67 %
55:45 d.r.
2x, 64 %
57:43 d.r.
Scheme 4. Scope of the iron-catalyzed synthesis of cyclopentanes and
cycloheptanes.
To gain mechanistic insights on the mechanism of this alkylation
reaction, a deuterium labeling experiment was performed
(Scheme 5). Under optimized conditions, the reaction using the
deuterated hexane-2,5-diol yielded 2s-d3 and 2s’-d3 in 71% as a
mixture of two diastereomers (d.r. = 58:42, the meso-
diastereomer as the major compound). Chemical yield is
comparable to the non-deuterated alkylation (Scheme 4).
obtained in
a 85:15 diastereomeric ratio (Scheme 3).
Gratifyingly, 1,2-disubstituted cyclohexanes 2n and 2o were
also produced with a good control of the diastereoselectvity
(d.r. = 90:10 to >95:5, Scheme 3). Finally, the reduction of (+)-
camphor acid led to a diol, which provided the ketone 2l upon
double alkylation in good yield (69%) and high diastereomeric
ratio (95:5). To unambiguously establish the atom connectivity
in 2l, single crystals were grown by slow evaporation of
methanol. Suitable single crystals were obtained and subjected
to X-ray diffraction. Thermal ellipsoid representation is shown
in Scheme 3 and highlight the syn-relationship between the CO
group, the methyl substituent and the hydrogen atom.
We then extended this work to the synthesis of cyclopentanes
and cycloheptanes and the use of 1,4- and 1,6-diols (Scheme 4).
Cyclopentane compounds 2p-u were isolated in moderate
yields (46-67%, Scheme 4). As observed previously with
substituted 1,5-diols, diastereoselectivity of the alkylation
depends on the position of the substituent. 1,2-disubstituted
Deuterium was incorporated in position
2 and 5 of
cyclopentanes for both diastereomers, suggesting that the diol
is the hydride source in the overall process and the mechanism
implies an inter- and an intramolecular alkylation via the
reduction of two enone intermediates (see the proposed
mechanism in the Supplementary Information, Scheme S2).
In conclusion, we have developed the first phosphine-free iron
complex-catalyzed synthesis of cycloalkanes using methyl
ketones and diols compounds via the hydrogen autotransfer
strategy. Various primary as well as secondary diols were
introduced in this alkylation and afforded cycloalkanes in
moderate to good yields. Labeling experiments confirm that the
diol was the source of hydrides in this process. These results
tend to promote the interest of phosphine-free iron complexes
in catalysis and encourage the development of new reactivities.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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Journal Name
H/D = 92/8
Org. Biomol. Chem., 2019, 17, 1595-1607. (c) B. Maji and M. K
H/D = 1/99
View Article Online
Barman, Synthesis, 2017, 49, 3377-3393.
O
DOI: 10.1039/D0CC05840H
D
D
10 (a) W. M Akhtar, C. B. Cheong, J. R. Frost, K. E. Christensen, N. G.
Stevenson and T. J. Donohoe, J. Am. Chem. Soc. 2017, 139, 2577-2580.
(b) P. Chakraborty, M. K Gangwar, B. Emayavaramban, E. Manoury, R.
Poli and B. Sundararaju, ChemSusChem, 2019, 12, 3463-3467. (c) L.
Bettoni, S. Gaillard and J.-L. Renaud, Org. Lett., 2020, 22, 2064-2069.
(d) S. Waiba, S. K. Jana, A. Jati, A. Jana and B. Maji, Chem. Commun.,
2020, 56, 8376-8379.
D
O
2s-d3
D
Fe1 (2 mol%), NaOH (4 equiv.)
OH
+
HO
+
D
H/D = 87/13
toluene (5 M), 130 °C, 40 h
71%
O
D
D
d.r. (2s-d3:2s'-d3)= 58:42
11 For an elegant approach with two secondary alcohols, see: (a) S.
Thiyagarajan and C. Gunanathan, J. Am. Chem. Soc., 2019, 141, 3822-
3827. (b) S. Thiyagarajan and C. Gunanathan, Synlett, 2019, 30, 2027-
2034.
D
H/D = 1/99
2s'-d3
Scheme 5. Deuterium labeling experiment.
12 (a) C. Schlepphorst, B. Maji and F. Glorius, ACS Catal. 2016, 6, 4184-
4188. (b) D. Shen, D. L. Poole, C. C. Shotton, A. F. Kornahrens, M. P.
Healy and T. J. Donohoe, Angew. Chem. Int. Ed. 2015, 54, 1642-1645.
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Stevenson, and T. J. Donohoe, J. Am. Chem. Soc. 2015, 137, 15664-
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Donohoe, Angew. Chem. Int. Ed. 2014, 53, 761-765. (e) S. M. A. H.
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Conflicts of interest
There are no conflicts to declare
Acknowledgements
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We gratefully acknowledge financial support from the
"Ministère de la Recherche et des Nouvelles Technologies",
Normandie Université, CNRS, "Région Normandie", and the
LABEX SynOrg (ANR-11-LABEX-0029). The authors warmly thank
Dr. Rémi Legay and Jean-François Lohier for the analytical
support.
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