Interactions of C?F Bonds with Hydridoboranes: Reduction, Borylation and Friedel–Crafts Alkylation

Article abstract of DOI:10.1002/chem.201804705

The stoichiometric reactions of the alkylfluorides 1-fluoroadamantane (Ad-F), fluorocyclohexane (Cy-F), 1-fluoropentane (Pent-F) and benzyl fluorides with secondary boranes pinacolborane (HBpin), catecholborane (HBcat), 9-borabicyclo(3.3.1)nonane (9-BBN)

Full text of DOI:10.1002/chem.201804705

A Journal of
Accepted Article
Title: Interactions of C-F bonds with hydridoboranes: Reduction,
Borylation and Friedel-Crafts Alkylation
Authors: Karlee Bamford, Saurabh Chitnis, Zheng-Wang Qu, and
Douglas Wade Stephan
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Interactions of C-F bonds with hydridoboranes: Reduction,
Borylation and Friedel-Crafts Alkylation
Karlee L. Bamford,a Saurabh S. Chitnis,a Zheng-wang Qu,b* and Douglas W. Stephan*[a]
Dedication ((optional))
Abstract: The stoichiometric reactions of the alkylfluorides 1-
fluoroadamantane (Ad-F), fluorocyclohexane (Cy-F), 1-
fluoropentane (Pent-F) and benzyl fluorides with secondary
boranes pinacolborane (HBpin), catecholborane (HBcat), 9-
borabicyclo(3.3.1)nonane (9-BBN) and Pier’s borane (HB(C6F5)2)
are described. While HBcat, 9-BBN and HB(C6F5)2 reduce Ad-F to
Ad-H, the latter borane was shown to react with secondary and
primary fluoroalkanes, affording C-F borylation, while benzyl
fluorides undergo Friedel-Crafts chemistry.
hydrodefluorination catalysis to the P(III) coordination compounds,
[(bipy)PPh][B(C6F5)4] and [(terpy)PPh][B(C6F5)4] (bipy = 2,2’-
bipyridine, terpy = 2,2':6',2"-terpyridine).[15]
The activation of carbon-fluorine (C-F) bonds is challenging
as they are the strongest single bond involving carbon (536
kJ/mol).[1] While the stability of C-F bonds has been advantageous
for use in agrochemicals[2] and pharmaceuticals,[2c, 3] strategies to
effect subsequent transformations C-F bonds are quite limited.
Transition metal systems have been shown to preferentially react
with C(sp2)-F bonds,[4] while proton-mediated Friedel-Crafts
reactions of polyaromatic monofluoro-arenes and benzyl fluorides
have been described by Siegel[5] and Paquin et al.,[6] respectively.
More recently a number of studies have described the activation
of C(sp3)-F bonds by interaction with the low energy LUMOs (p-
orbital) of main group electrophiles.[7] For example,
hydrodefluorination has been well documented for a variety of
silylium and disilyl cations.[8] Similarly, stoichiometric alkylation of
the CF3 functional group has been effected using aluminum alkyl
species,[9] an alumenium cation[10] or aluminum-chlorofluoride
species.[11]
Figure 1. Selected main group systems that react with C-F bonds.
The possibility of borane-mediated C-F bond
activation was first revealed in 1943[16] with the use of BF3 and
was furthered in the seminal work of Olah.[17] The use of Et3NBF3
in dehydrofluorination reactions was later described by
Knunyants[18] in 1975. N-heterocyclic carbene-borane adducts
have also been shown to affect haloalkane C-X (X = Cl, Br, I) bond
reduction, albeit under forcing conditions (140 °C), although this
reactivity was not extended to C-F bonds.[19] In 2012, we reported
[20]
the use of the Lewis acid, B(C6F5)3 for hydrodefluorination of
fluoroalkanes. Despite these findings, the fundamental reactivity
of hydridoboranes with C(sp3)-F bonds has not been explored.[21]
Herein, we report the facile reactions of hydridoboranes with a
representative set of fluorinated organic substrates,
demonstrating the ability of these readily accessible reagents to
effect stoichiometric reduction, borylation or Friedel-Crafts
reactivity of C-F bonds.
In 2013, we developed the electrophilic phosphonium cation
(EPC), [(C6F5)3PF][B(C6F5)4][12] in which the Lewis acidity is
derived from the σ*-orbital. This EPC is an effective catalyst for
the hydrodefluorination of fluoroalkanes and was subsequently
employed to mediate Friedel-Crafts alkylation of arenes using
alkyl-CF3 and benzyl fluoride substrates. In a related sense,
Gabbaï and coworkers[13] developed the air-stable species
[(C6F5)4Sb][B(C6F5)4] for hydrodefluorination catalysis. In further
related work, Greb[14] has developed the silicon-based species
[Si(O2C6Cl4)2], which becomes hypervalent in exhibiting its affinity
for fluoride. In very recent work, we have extended such C-F bond
In initially probing stoichiometric C-F reduction using
hydridoboranes, pinacolborane (HBpin) was combined with 1-
fluoroadamantane (Ad-F), fluorocyclohexane (Cy-F), or 1-
fluoropentane (Pent-F) in CD2Cl2 in J-Young NMR tubes. In all
cases, HBpin was unreactive at ambient temperature or upon
heating to 55-80 °C. In contrast, the tertiary fluoride, Ad-F and
catecholborane (HBcat) reacted at ambient temperature in < 10
mins, affording adamantane and FBcat as the major products as
evidenced by 1H, 19F and 11B NMR spectroscopy. The similar
conversion of Ad-F to adamantane was observed for the reaction
with 9-borabicyclo(3.3.1)nonane (9-BBN), although this required
24 h at ambient temperature. In the case of Pier’s borane,
HB(C6F5)2, 11B NMR spectroscopy showed resonances at 43.2
and 22.2 ppm attributable to the species FB(C6F5)2 and F2B(C6F5),
respectively. This was confirmed by the independent generation
of FB(C6F5)2 and F2B(C6F5) from HB(C6F5)2 and SbF3 following
[a]
Ms. Karlee Bamford, Dr. Saurabh Chitnis and Professor Dr. D.W.
Stephan
Department of Chemistry, University of Toronto,
80 St. George St., Toronto, Ontario, Canada M5S3H6
E-mail: dstephan@chem.utoronto.ca
[b]
Dr. Zheng-Wang Qu
Mulliken Center for Theoretical Chemistry, Institut fuer Physikalische
und Theoretische Chemie,Universitaet Bonn, Beringstrasse 4, D-
53115 Bonn, Germany
E-mail: qu@thch.uni-bonn.de
Supporting information for this article is given via a link at the end of
the document.
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1
the method of Chambers and Chivers.[22] Monitoring by H, 11B,
and 19F NMR spectroscopy revealed HB(C6F5)2 reacts with Ad-F
at ambient temperatures to give the rapid formation of
revealed the consumption of only the Cy-F substrate (See ESI)
after 10 minutes. This preferential cleavage of C-F bonds
demonstrates reactivity that is orthogonal to that of traditional
metal-derived systems where reactions are selective to C-X (X =
Cl, Br, I) bonds.
adamantane and C6F5-adamantyl in
observations are consistent with
a
77:23 ratio. These
mechanism involving
a
coordination of the Ad-F to borane prompting F/H or F/C6F5
metathesis in processes that are apparently competitive.
Scheme 3 Reactions of boranes with Pent-F.
Scheme 1 Reactions of hydridoboranes with Ad-F (x = 1 or 2).
The primary alkyl fluoride Pent-F was unreactive with HBpin,
HBcat and 9-BBN while it reacted with HB(C6F5)2 over 24 h at
The secondary fluoride Cy-F was unreactive with HBcat at
ambient temperature, whereas it reacted quantitatively with 9-
BBN over 24 h at ambient temperature, effecting the formation of
cyclohexene, H2 and 9-F-9-BBN. In a similar, albeit considerably
faster reaction, Cy-F and HB(C6F5)2 reacted yielding CyB(C6F5)2
as the dominant product. While treatment of Cy-F with one
equivalent of HB(C6F5)2 afforded a mixture of cyclohexene,
cyclohexane and CyB(C6F5)2, the use of two equivalents of
HB(C6F5)2, afforded CyB(C6F5)2 in 97% yield with a 3 % yield of
cyclohexane. The former product results from the hydroboration
of cyclohexene and gives rise to the characteristic resonance at
73.1 ppm by 11B NMR spectroscopy.[23] These observations
suggest an initial borane-fluoroalkane interaction that prompts
defluorination with concurrent loss of H2. This is consistent with
the increased acidity of the proton on the β-carbon and the
observed deprotonation product, cyclohexene. It is noteworthy
that no evidence of cyclohexyl-cation rearrangement to
methylcyclopentene was observed, inferring that either
dehydrofluorination is a concerted process or that deprotonation
of the cyclohexyl-cation by [HBF(C6F5)2]- is fast relative to
carbocation rearrangement. Regardless, the formation of
CyB(C6F5)2 provides a rare, if not unprecedented, example of
uncatalyzed C-F borylation and stands in marked contrast to the
hydrodefluorination chemistry observed for reactions of
hydridoalanes and fluoroalkanes.[24]
1
ambient temperature. H, 11B, and 19F NMR spectroscopy were
consistent with the formation of H2 and a mixture of five new
boron-containing species exhibiting 11B chemical shifts at 75.7,
59.4, 52.4, 43.2 and 22.2 ppm. The first three resonances were
attributed to the products of HB(C6F5)2 hydroboration of 1-pentene
and 2-pentene,[25] while the latter two resonances arise from
FB(C6F5)2 and F2B(C6F5), respectively. Performing the reaction
with two equivalents of borane provide the isomeric hydroboration
products in 32%, 28% and 37% yields, respectively (Scheme 3).
These observations are consistent with dehydrofluorination and
subsequent hydroboration, analogous to the C-F borylation
observed with Cy-F. While the formation of an isomeric mixture of
pentenes could suggest the intermediacy of a primary carbocation,
retrohydroboration is also a viable explanation.[26]
Substrates in which β-hydrogen atoms are absent were also
examined. To this end, the reactions of the benzyl fluorides p-
PhC6H4CH2F or o-PhC6H4CH2F with hydridoboranes were also
probed in CH2Cl2. For 9-BBN, monitoring the reaction mixtures by
19F NMR spectroscopy confirmed the formation of 9-F-9-BBN,
while broadened signals in 1H NMR spectra (3.80-4.00 ppm) were
consistent with the formation of oligomeric poly(arylmethylenes).
This interpretation was supported by mass spectroscopic data
showing low molecular weight oligomeric species (m/z < 1200,
see ESI). Vigorous bubbling of reaction mixtures was confirmed
to be the result of H2 loss by 1H NMR spectroscopy. Collectively,
these observations are reminiscent of the BF3-catalyzed
alkylation of benzene using fluoroalkanes that was previously
described by Olah.[27] A similar oligomerization result was
obtained using the borane HB(C6F5)2.
The formation of oligomeric products strongly suggests that
fluoride abstraction prompts the transient generation of a benzyl
carbocation which then undergoes Friedel-Crafts benzylation of
unreacted benzyl fluoride with the subsequent liberation of H2. To
further support this notion, the reactions of HB(C6F5)2 with o- and
p-PhC6H4CH2F were repeated in an arene (C6D6) solvent. In this
case, the Friedel-Crafts alkylation of the solvent was seen
affording selectively the respective products o- and p-
PhC6H4CH2(C6D5), as evidenced by NMR spectroscopy (See ESI).
Scheme 2 Reactions of hydridoboranes with Cy-F (x = 1 or 2).
The corresponding reactions of HB(C6F5)2 with chloro-,
bromo- and iodo-cyclohexanes showed no reaction at ambient
conditions. Indeed, a competition experiment using a 1:1:1:1
mixture of Cy-X (X = F, Cl, Br, I) with HB(C6F5)2 (2 equivalents)
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The analogous reaction using 9-BBN yields the respective
products o- and p-PhC6H4CH2(C6D5), however the reaction takes
considerably longer, 3 or 36 hours, respectively. The benzylations
of toluene, fluorobenzene, chlorobenzene and bromobenzene
affording p-PhC6H4CH2(C6H4R) (R = Me, F, Cl Br) were also
achieved quantitatively using HB(C6F5)2, with the formation of two
substitutional isomers (ortho, para) in each case, under similar
conditions in neat arene (See ESI).
(see ESI), whereas Ad-C6F5 is experimentally observed in 23%
yield.
Scheme 4 Reactions of boranes with o- or p-PhC6H4CH2F.
Efforts to activate C-F bonds of polyfluorinated substrates
were also undertaken. Reactions of 9-BBN or HB(C6F5)2 with
α,α,α-trifluorotoluene,
(trifluoromethyl)cyclohexane,
2H,3H-
decafluoropentane or octadecafluorodecahydronaphthalene
gave no reaction even after prolonged heating to 80 °C.
Presumably, the decreased Lewis basicity of the C-F bonds in
these substrates precludes interaction with the Lewis acidic
hydridoborane that initiates the reactions above.
To probe the mechanisms of these borane/C-F reactions,
DFT calculations at the TPSS-D3/def2-QZVP + COSMO-RS //
28]
TPSS-D3/def2-TZVP + COSMO level[9a,
were performed.
Reactions of dimeric borane [(C6F5)2BH]2 with Ad-F, Cy-F and Bn-
F (benzyl fluoride) in CH2Cl2 solution were computed (Figure 2).
In all cases, the initial dissociation of diborane into two monomers
is the rate-limiting step and 7.0 kcal/mol endergonic over a barrier
(via TS1) of 17.6 kcal/mol. For comparison, the initial dissociation
of diborane (9-BBN)2 into two monomers 9-BBN is 17.6 kcal/mol
endergonic over a higher barrier of 22.5 kcal/mol, consistent with
its slower reactions with C-F bonds. The adduct (Ad-
F)·(C6F5)2BH·exhibits considerable ionic character with elongated
B-F and F-C bonds (1.596 and 1.633 Å, respectively). Both
hydride and C6F5 transfer from the borane to Ad occurs via
contact-ion-pair-like transition structures TS2 and TS3 affording
Ad-H and (C6F5)2BF or Ad-C6F5 and (C6F5)BFH, respectively.
Consistent with experiment, the former hydride transfer is
computed to be 1.5 kcal/mol kinetically more favourable. The
transient borane (C6F5)BFH either dimerizes to [(C6F5)BFH]2 or
disproportionates to minor amounts of (C6F5)BF2 and (C6F5)BH2
via a bimolecular H/F exchange process. While the separated ion
pair [Ad]+[(C6F5)2BHF]- is also thermodynamically accessible (via
TS4-h) from the adduct (Ad-F)·(C6F5)2BH, this is inconsistent with
experimental data. Hydride transfer to give Ad-H (via TS4)[29] is
computed to be 15 kcal/mol higher barrier than for aryl transfer
Figure 2. DFT-computed free energy paths (G at 298 K for each
step in kcal/mol, barrier in parentheses) for typical reactions of
dimeric borane [(C6F5)2BH]2 with (A) Ad-F, (B) Cy-F and (C) Bn-F
in CH2Cl2 solution, obtained at the TPSS-D3/def2-QZVP +
COSMO-RS // TPSS-D3/def2-TZVP + COSMO level of theory.
Cye = cyclohexene. In depicting the cores of the transition states,
substituents on B and C are omitted for clarity. Selected bond
lengths (in Å) are shown.
The adduct (Cy-F)·(C6F5)2BH is less ionic in nature with a
longer B-F but a shorter F-C distances (1.784 and 1.515 Å,
respectively). Hydride transfer from (C6F5)2BH to the β-hydrogen
(proton) of Cy proceeds via the contact-ion-pair-like transition
structures TS5 yielding H2 gas and cyclohexene (Cye). Borane
dimer dissociation is again rate-limiting. Side-reactions such as
aryl and hydride transfer from borane (C6F5)2BH to the β-
hydrogen (proton) were computed to be kinetically less
competitive by 10.1 and 8.3 kcal/mol (see ESI). Similarly, a
pathway involving a separated ion pair [Cy]+[(C6F5)2BHF]- is high-
energy and thus not favoured. The subsequent addition of borane
to Cye to form the main product CyB(C6F5)2 is 10.0 kcal/mol
exergonic over a rather low barrier (via TS6) of only 9.2 kcal/mol
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higher overall barrier of 23.8 kcal/mol is supported (see ESI) for
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In summary, we have uncovered that hydridoboranes can
be used to reduce C(sp3)-F bonds at ambient conditions without
the use of catalysts or initiators. In particular, the electrophilic
borane HB(C6F5)2 was shown to be reactive with secondary and
primary fluoroalkanes, affording initial olefinic products via
dehydrofluorination, which in the presence of additional
hydridoborane affords a net C-F borylation. This constitutes, to
the best of our knowledge, the only example of catalyst-free
C(sp3)-F borylation involving a neutral hydridoborane reagent.
While 9-BBN and (C6F5)2BH effect hydrodefluorination of tertiary
C-F bonds, benzyl fluorides undergo Friedel-Crafts chemistry in
the presence of arene solvents. Overall, this provides new routes
to C-F borylation and room temperature Friedel-Crafts chemistry.
We are continuing to develop strategies and applications using
main group species to effect chemistry of C-F bonds.
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Acknowledgements
NSERC of Canada is thanked for financial support. D.W.S is
grateful for the award of a Canada Research Chair and a Visiting
Einstein Fellowship at TU Berlin. K.B is grateful for the support of
an NSERC CGS-D scholarship. Z.W.Q. acknowledges financial
support from the Deutsche Forschungsgemeinschaft in the
framework of the Leibniz prize to Prof. Stefan Grimme.
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Keywords: hydridoboranes • Alkyl-fluorides • C-F reduction •
borylation • Friedel-Crafts
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Chemistry - A European Journal
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[29]S. Mummadi, D. K. Unruh, J. Zhao, S. Li, C. Krempner, J Am Chem Soc
2016, 138, 3286-3289.
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10.1002/chem.201804705
Chemistry - A European Journal
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Interactions of C-F bonds
with
Reduction, Borylation and
Friedel-Crafts Alkylation:
Hydridoboranes react with
primary, secondary and
hydridoboranes:
Karlee Bamford, Saurabh
Chitnis, Zheng-Wang Qu* and
Douglas W. Stephan*
Page No. – Page No.
tertiary C-F bonds under
ambient conditions affording
Interactions of C-F bonds with
hydridoboranes: Reduction,
Borylation and Friedel-Crafts
Alkylation
either
dehydrofluorination,
hydrodefluorination,
C-F
borylation or Friedel-Crafts
chemistry alkylation.
This article is protected by copyright. All rights reserved.