The phosphinoboration of acyl chlorides

Article abstract of DOI:10.1039/d0dt00579g

This investigation examines the reactivity of phosphinoboronate esters Ph₂PBpin (pin = 1,2-O₂C₂Me₄) and Ph₂PBcat (cat = 1,2-O₂C₆H₄), as well as other phosphinoboron species, with various aryl and aliphatic acyl chlorides. These reactions proceed smoothly to give acyl phosphines of the type RC(O)PR′₂ along with loss of a boron-chloride compound. In some cases, a second equivalent of the phosphinoboron species can add to the CO double bond at elevated temperatures to give the corresponding diphosphines RC(OBR′′₂)(PR′₂)₂. These ambiphilic diphosphines behave like substituted (1,1-bis(diphenylphosphino)methane) derivatives in a reaction of PhC(OBpin)(PPh₂)₂ (2a) with (η⁵-C₉H₇)Rh(η²-coe)₂ (coe = cis-cyclooctene) affording the indenyl rhodium complex (η⁵-C₉H₇)Rh(PhC(OBpin)(PPh₂)₂) (3a) where the phosphines are bound to the metal centre in a κ²-P,P bidentate manner.

Full text of DOI:10.1039/d0dt00579g

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Trofimova, J. LaFortune, C. M. Vogels, S. Geier, J. F. Binder, C. Macdonald, D. Stephan and S. Westcott,
Dalton Trans., 2020, DOI: 10.1039/D0DT00579G.
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Number 10
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ISSN 0306-0012
COMMUNICATION
Douglas W. Stephen et al.
N-Heterocyclic carbene stabilized parent sulfenyl, selenenyl,
and tellurenyl cations (XH , X = S, Se, Te)
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Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
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DOI: 10.1039/D0DT00579G
Dalton Transactions
ARTICLE
The Phosphinoboration of Acyl Chlorides
a
b
b
a
a
c,d
Maia C. Murphy, Alina Trofimova, James H. W. LaFortune, Christopher M. Vogels, Stephen J. Geier, Justin F. Binder,
Received 00th January 20xx,
Accepted 00th January 20xx
Charles L. B. Macdonald,c,d Douglas W. Stephan* and Stephen A. Westcott*
b
a
This investigation examines the reactivity of phosphinoboronate esters Ph
,2-O
proceed smoothly to give acyl phosphines of the type RC(O)PR’
cases, a second equivalent of the phosphinoboron species can add to the C=O double bond at elevated temperatures to
give the corresponding diphosphines RC(OBR” )(PR’ These ambiphilic diphosphines behave like substituted 1,1-
2
PBpin (pin = 1,2-O
2
C
2
Me
4
) and Ph
2
PBcat (cat =
DOI: 10.1039/x0xx00000x
1
2
C
H
6 4
), as well as other phosphinoboron species, with various aryl and aliphatic acyl chlorides. These reactions
along with loss of a boron-chloride compound. In some
2
2
2 2
) .
5
2
bis(diphenylphosphino)methane) derivatives in a reaction of PhC(OBpin)(PPh
2
)
2
(2a) with (η -C
9 7 2
H )Rh(η -coe) (coe = cis-
5
cyclooctene) afforded the indenyl rhodium complex (η -C
9 7
H )Rh(PhC(OBpin)(PPh
2
)
2
) (3a) where the phosphines are bound
2
to the metal centre in a κ -P,P bidentate manner.
compounds has tremendous potential in frustrated Lewis pair (FLP)
1
1
Introduction
Over the past few decades there has been considerable interest in
the chemistry of B-E-containing compounds (E = H, B, Si, O, N, etc),
especially in addition reactions with unsaturated small molecules
chemistry. Indeed, we have recently reported on the application
of the BNNP FLPs derived from phosphinoborane addition to
1
2
diazobenzene chemistry.
1
such as alkenes, alkynes, carbonyl groups and imines. Although
Bpin
O
C
2
3
hydroborations (E = H), diborations (E = B), and silylborations (E =
N
PPh2
R
C
N
NR
C
Bpin
4
Si) are well-known reactions, the analogous chemistry with boron-
Ph2P
CO2
O
main group compounds where E contains a lone pair of electrons is
R
NR
5
much less studied. Indeed, only recently have oxyboration and
PPh2
6
NR"
C
aminoboration reactions drawn much attention. Significant π-
R"
Bpin
N
C
P
N
dative bonding from the heteroatoms directly bound to boron can
increase the stability of these species and therefore reduce their
reactivities in the corresponding addition reactions. Our groups
have designed a series of phosphinoboronate esters (E = P)
containing primarily single B-P bonds that have shown remarkable
activity in uncatalysed or base-mediated addition of aldehydes,
ketones, imines, N-heterocyclic aromatics, carbodiimide derivatives,
and even with carbon dioxide (Scheme 1). A concurrent study by
Su and co-workers reported cycloaddition reactions of simple B=P
compounds to dienes and nitriles where the corresponding
R
R'
Ph
Ph
B
O
R
PPh2
N
O
R'
7
O
C
Bpin
Ph2PBpin
R
R'
RNNR
Bpin
OBpin
C
R
R
N
R
PPh2
R'
N
PPh2
8
Scheme 1 The phosphinoboration of carbonyl groups, imines, carbodiimides, carbon
dioxide, pyridine, and diazobenzene using Ph Bpin.
2
9
products maintained a single B-P bond. In that study, they also
Acyl phosphines are used in industry as photoinitiators for
radical-induced polymerization reactions13 for automotive coatings,
adhesives, latex composition kits, and various dental and
orthodontic materials.14 Known methodologies to such
photoinitiators exploit pyrophoric, toxic, expensive reagents that
are often difficult to handle.15 For example, the groups of Liotta,
Becker, Grützmacher and Mézailles have developed methods to
acylphosphines based on the chemistry of PH and MPH (M = Li,
reported the reduction of benzophenone. Interestingly, Grubba and
co-workers
have
elegantly
designed
a
family
of
diaminophosphinoboranes for the capture and reduction of carbon
1
0
dioxide. The ability to introduce both a Lewis basic phosphide
PR ) and a Lewis acidic boryl (BR ) group into a variety of
(
2
2
a. Department of Chemistry and Biochemistry, Mount Allison University, Sackville,
NB E4L 1G8, Canada.
3
2
Na, K) as nucleophiles.16 More recently, P-carbonyl derivatives have
b.
Department of Chemistry, University of Toronto, Toronto, ON M5S 3H6, Canada.
Department of Chemistry and Biochemistry, University of Windsor, Windsor, ON
c.
-
17
been prepared from reactions of salts of [PCO] anion, while
Cummins et. al. have described a synthetic route based on a
masked phosphinidene reagent.18 In the present manuscript, we
N9B 3P4, Canada.
d.
Department of Chemistry, Carleton University, Ottawa, ON K1S 5B6, Canada.
Electronic Supplementary Information (ESI) available: Complete spectroscopic data
is available at DOI:
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Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
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ARTICLE
Journal Name
2
document the utility of phosphinoboranes in reactions with acyl- to benzoyl chloride. As expected, reactions between Ph PBcat (cat
View Article Online
chlorides as a route to acyl phosphines. Further reactions with = 1,2-O
2
C
6 4
H ) or Ph
2
BMes
2
(Mes = mesityl)DaOnId: 1P0.h1C03(O9/)DC0l DaTls0o05g7a9vGe
phosphinoboranes to give addition across the carbonyl fragment 1a with complete conversion, along with the concomitant
are also probed as an avenue to uniquely derived diphosphino- formation of ClBcat and ClBMes , respectively. Altering the
substituents on the phosphorus group allowed the generation of
the acyl phosphines PhC(O)PMes (1b) and PhC(O)Pt-Bu (1c) using
Mes PBcat, t-Bu PBcat, or t-Bu PBMes . Compounds 1b and 1c
2
methanes.
2
2
2
2
2
2
Results and Discussion
were characterized fully using multinuclear NMR spectroscopy and
Our initial attempts focussed on reactions involving benzoyl elemental analysis. The 31P{ H} NMR spectra showed a sharp singlet
1
chloride, PhC(O)Cl, and Ph
proceeded smoothly at room temperature to give known sterically encumbered electron-withdrawing mesityl derivative 1b is
(1a)19 and ClBpin20 without the need for a found at -2.9 ppm while the bulky electron-donating t-butyl
compounds PhC(O)PPh
catalyst precursor or additional base to activate the P-B bond derivative 1c is observed at 39.5 ppm. A single-crystal X-ray
2 2 2 4
PBpin (pin = 1,2-O C Me
). The reaction for these compounds with quite different chemical shifts, the
2
(
Scheme 2a). The formation of these products presumably arises diffraction study on 1b confirmed the connectivity (Figure 1). The
1
8-
either from a sigma-bond type metathesis reaction involving a four- molecular metrics are well within the range for related structures.
2
1
centred transition state or via initial addition of the
phosphinoboronate ester to the C=O double bond followed by
The corresponding reactions of aliphatic hexanoyl chloride and
PBpin
multinuclear NMR spectroscopy, however, showed no evidence for proceeded smoothly at room temperature to give 1d and 1e,
elimination of the ClBpin species. Monitoring the reaction by the ester derivative propargyl chloroformate with Ph
2
this latter pathway.
respectively. These reactions were quantitative affording the new
phosphorous-containing species with complete conversion of the
starting acyl chloride (Scheme 2). Reaction of trans-cinnamoyl
O
O
chloride with Ph PBpin gave a complicated mixture of products
2
(a)
including the expected acyl phosphine 1f, along with ClBpin.
Unfortunately, reactions of Ph PBpin with 9-fluorenone-4-carbonyl
2
rt
Cl
+
PR2
R2PBR'2
-
ClBR'2
chloride also gave a mixture of products arising from competing
addition to the ketone group along with decomposition of the
starting phosphinoboronate ester.
1
1
1
a: R = Ph
b; R = Mes
c; R = t-Bu
O
O
(b)
O
P
P
P
Ph
Ph
Ph
Ph
Ph
Ph
O
1d
1e
Ph
1f
BR'2
Scheme 2 The phosphinoboration of acyl chlorides.
O
O
R2PBR'2
PR2
PR2
PR2
2a: R = Ph, R' = pin
1
O
P
a: R = Ph
2
b: R = Ph, R' = cat
pinB
Bpin
P
Ph
Ph
1d
1f
O
P
Ph2PBpin
P
Ph
Ph
2d
Ph
Ph
Ph
Ph
2f
Ph
Scheme 3 The phosphinoboration of acyl phosphines.
Further addition of Ph
2
PBpin to 1a proceeded slowly at elevated
temperatures to give the corresponding diphosphine 2a (Scheme
3
). These same conditions could be used on aliphatic acyl phosphine
1
d to selectively give 2d. Attempts to facilitate the similar addition
2
of a second equivalent of Ph PBpin to the alkyne group 1e proved
unsuccessful, even at elevated temperatures and with the use of a
Rh catalyst. This lack of reactivity is in stark contrast to our
previous study using terminal aromatic alkynes where the 1,1-
Fig. 1 The molecular structure of 1b drawn at the 50% probability level with hydrogen
atoms omitted for clarity. Selected bond distances (Å) and angles ( ): P(1)-C(8)
o
1
1
.8306(19), P(1)-C(17) 1.8356(18), P(1)-C(7) 1.860(2), O(1)-C(7) 1.219(2), C(1)-C(7) addition products were prepared by employing rhodium
.500(2); C(8)-P(1)-C(17) 110.68(8), C(8)-P(1)-C(7) 113.72(8), C(17)-P(1)-C(7) 102.35(9),
precatalysts.8d The diphosphine derived by addition to in-situ
O(1)-C(7)-P(1) 118.94(14), C(1)-C(7)-P(1) 118.63(13).
generated 1f could eventually be generated under these harsher
conditions but resulted in a mixture of 1,2- and 1,4-addition
products; the latter species 2f being the major species in solution.
The generality of this reaction was subsequently probed with
the investigation of the addition of other phosphinoboron species
2
| Dalton Trans., 2019, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
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Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
Journal Name
ARTICLE
The addition of the more Lewis acidic phosphinoboronate ester weak interaction of the P(2) atom with the Lewis aciVdiebwoArrtoicnle aOtnolinme
Ph
PBcat to acylphosphine 1a also proceeded at room temperature which are somewhat close between the tDwOoI: 1a0t.130.3294/D6(02D)T0Å0. 5T7h9Gis
2
to give the corresponding addition product 2b as the only new suggests that this compound could have potential applications in
boron-containing product in solution.
FLP chemistry. 11,22 In the case of 2f, the bond distances and angles
are typical for related species and the short C(20)-C(21) distance of
1
.328(3) Å and the large C(21)-C(20)-C(13) angle of 127(2)o are
consistent with a C=C double bond.
Efforts to extend such additions to sterically-encumbered
diphosphines via additions of Ph
2 2 2 2
PBMes , t-Bu PBMes , and t-
Bu PBcat to 1a or 1c proved unsuccessful. However, related
2
additions of TolSBpin and PhSeBpin23 to acyl chlorides were
effective. For example, reaction of PhC(O)Cl with these reagents
afforded ClBpin and the known derivatives PhC(O)STol and
PhC(O)SePh respectively,24 although higher temperatures and
extended times were required in comparison to the analogous
2
reactions of Ph PBpin (Scheme 4).
O
O
rt
Cl
ChR
+
RChBpin
-
ClBpin
Ch = S, R = p-tolyl
Ch = Se, R = Ph
Scheme 4 Synthesis of acyl chalcogenides.
Fig. 2 The molecular structure of 2b drawn at the 50% probability level with hydrogen
atoms omitted for clarity. Selected bond distances (Å) and angles ( ): P(1)-C(25)
o
1
.917(2), P(2)-C(25) 1.940(2), B(1)-O(1) 1.353(3), B(1)-O(2) 1.392(3), B(1)-O(3) 1.396(3);
Bpin
O
O(1)-B(1)-O(2) 117.6(2), O(1)-B(1)-O(3) 129.6(2), O(2)-B(1)-O(3) 112.51(18), P(1)-C(25)-
P(2) 102.83(10), B(1)-O(1)-C(25) 132.31(17).
toluene
00 oC, 6 h
1
Rh
+
Ph
PPh2
Rh
-
2 coe
Ph2P
pinB
PPh2
Ph
PPh2
a
2
O
3a
Scheme 5 Synthesis of indenyl rhodium complex 3a.
Fig. 3 The molecular structure of 2f drawn at the 50% probability level with hydrogen
o
atoms omitted for clarity. Selected bond distances (Å) and angles ( ): P(1)-C(13)
1
.883(2), P(2)-C(21) 1.821(2), O(1)-B(1) 1.363(3), O(2)-B(1) 1.367(3), O(3)-B(1) 1.359(3),
C(20)-C(21) 1.328(3), C(13)-C(20) 1.505(3); O(3)-B(1)-O(1) 126.3(2), O(3)-B(1)-O(2)
15.0(2), O(1)-B(1)-O(2) 118.6(2), C(21)-C(20)-C(13) 127.0(2), C(20)-C(21)-O(1) 121.5(2),
1
C(20)-C(21)-P(2) 120.90(18).
Fig. 4 The molecular structure of 3a drawn at the 50% probability level with
hydrogen atoms omitted for clarity. Selected bond distances (Å) and angles
(o): Rh(1)-P(1) 2.1847(7), Rh(1)-P(2) 2.1991(7), Rh(1)-C(48) 2.277(3), Rh(1)-
C(40) 2.253(3), Rh(1)-C(41) 2.221(3), Rh(1)-C(42) 2.388(3), Rh(1)-C(47)
In support of the formulation of these products, X-ray
diffraction studies of 2b and the 1,4-addition product 2f were
performed (Figures 2, 3). In the case of 2b, it is interesting to note
that there are two distinct P-C bond distances with the P(1)-C(25)
bond length of 1.917(2) Å while the P(2)—C(25) bond is slightly
elongated at 1.940(2) Å. This disparity is thought to arise from a
2
.406(3); P(1)-Rh(1)-P(2) 75.08(2).
Access to elementally pure samples of 2a prompted interest in
its coordination chemistry. This together with our long-standing
This journal is © The Royal Society of Chemistry 20xx
Dalton Trans, 2019, 00, 1-3 | 3
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Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
Page 4 of 8
ARTICLE
Journal Name
interest in indenyl rhodium complexes as pre-catalysts for were measured uncorrected with a Stuart SMP30 apparatus.
View Article Online
numerous chemical transformations25 led to the reaction of (η5- Elemental analyses for carbon and hydrogen were performed
DOI: 10.1039/D0DT00579G
2
C
9
H
7
)Rh(η -coe)
2
(coe = cis-cyclooctene) with 2a. The resulting at the University of Toronto using a PerkinElmer 2400 Series II
)Rh(PhC(OBpin)(PPh
) 3a was formed as the only CHNS analyser.
5
complex (η -C
9
H
7
2 2
)
new phosphorous-containing species in solution along with the
concomitant liberation of cyclooctene (Scheme 5). Complex 3a was
easily isolated via precipitation and characterized fully using
Synthesis of PhC(O)PPh
the given phosphinoborane (Ph
Ph PBMes ) (0.1 mmol) was prepared in CH
solution of benzoyl chloride (14 mg, 0.1 mmol) in CH
was added at ambient temperature and the reaction mixture
was left to stir for 24 h. The solution was then dried in vacuo,
2
(1a).12 In a 20 mL vial, a solution of
PBpin, Ph PBcat or
Cl (3 mL).
Cl (3 mL)
2
2
multinuclear NMR spectroscopy and elemental analysis. The 31P{1H}
2
2
2
2
A
2
2
NMR spectrum for 3a displays a doublet at 44.0 ppm with a
coupling constant of JPRh = 198 Hz, typical for indenyl Rh(I)
complexes. 25 The 11B NMR spectrum shows a broad peak at 20
recrystallized by layering with pentane and CH
and washed with cold pentane (3 x 2 mL) to afford a yellow
solid (Ph PBpin: 28 mg, 95% isolated yield, Ph PBcat: 28 mg,
6% isolated yield, Ph PBMes
: 27 mg, 94% isolated yield). 1H
NMR (400 MHz, CDCl ) δ: 7.97 (m, 2H, Ar), 7.48-7.32 (ov m,
3H, Ar); C{ H} NMR (100 MHz, CDCl ) δ: 213.0 (d, JCP = 37
Hz), 139.3 (d, JCP = 35 Hz), 135.0 (d, JCP = 19 Hz), 133.3, 132.8
2 2
Cl , decanted
1
13
1
ppm consistent with a three coordinate boron atom. H and C{ H}
NMR data for the indenyl ring suggest there is the expected slight
2
2
5
3
slip-fold distortion away from the η -isomer towards the η -allylic
form.25,26
9
2
2
3
The structure of 3a was confirmed in the solid state via a single
crystal X-ray diffraction study (Figure 4). These data confirm the
bidentate chelation of 2a to Rh with no significant interaction of the
boron atom with the metal centre. In the solid state it appears the
indenyl ligand displays a pronounced slippage away from the planar
13
1
1
3
(
9
d, JCP = 6 Hz), 129.6, 128.8 (d, JCP = 9 Hz), 128.6, 128.4 (d, JCP =
Hz); P{ H} NMR (162 MHz, CDCl ) δ: 14.1.
3
31
1
η5-indenyl ring as the Rh-C distances to the quaternary carbons Synthesis of PhC(O)PMes (1b). In a 20 mL vial, a solution of
2
C(42) and C(47) are longer than the ‘allylic’ CH carbons C(41), C(40) Mes
and C(48) where the slip parameter difference is ΔM-C = 0.147(3) Å. A solution of benzoyl chloride (14 mg, 0.1 mmol) in CH
2
PBcat (38.8 mg, 0.1 mmol) was prepared in CH
2
Cl
2
(3 mL).
Cl (3
2
2
mL) was added at ambient temperature and the reaction
mixture was left to stir for 24 h. The solution was then dried in
The acute bite angle of the two phosphorous atoms of 75.08(2) is
similar to other related κ -P,P-(dppm)Rh(I) complexes.
2
27
vacuo and washed with cold pentane (3 x 2 mL) to afford a
1
yellow oil. Yield: 35 mg (94%). H NMR (500 MHz, C
6 6
D ) δ: 8.11
(
1
2
m, 2H, Ar), 6.98-6.89 (ov m, 3H, Ar), 6.68 (m, 4H, Ar), 2.35 (s,
Experimental
Materials and methods
1
3
1
2H, CH
3 3 6 6
), 2.00 (s, 6H, CH ); C{ H} NMR (125 MHz, C D ) δ:
11.0 (d, JCP = 37 Hz), 143.9 (d, JCP = 15 Hz), 141.3 (d, JCP = 43
All manipulations were performed in a MB Unilab glove box
produced by MBraun or using standard Schlenk techniques
Hz), 139.4 (d, JCP = 1 Hz), 132.6 (d, JCP = 2 Hz), 130.3 (d, JCP = 5
Hz), 128.6 (d, JCP = 1 Hz), 128.4, 128.0 (d, JCP = 2 Hz), 23.5 (d, JCP
2
under an inert atmosphere of anhydrous N . Reagents and
14 Hz), 21.0. 31P{ H} NMR (162 MHz, C
1
=
6 6
D
) δ: -2.9. Anal.
H27OP (374.46 g∙mol ): C, 80.19; H, 7.27. Found:
solvents were obtained from Sigma-Aldrich, Strem Chemicals,
TCI Chemicals or Alfa Aesar. Dry, oxygen-free solvents
-1
calcd. for C25
C, 80.07; H, 7.34.
(dichloromethane, toluene, and n-pentane) were prepared
using an Innovative Technologies solvent purification system
or deoxygenated and distilled over sodium benzophenone.
Synthesis of PhC(O)PtBu
given phosphinoborane (t-Bu
mmol) was prepared in CH Cl
2
(1c). In a 20 mL vial, a solution of the
PBcat or t-Bu PBMes ) (0.1
(3 mL). A solution of benzoyl
chloride (14 mg, 0.1 mmol) in CH Cl (3 mL) was added at
2
2
2
CDCl
stored over 3 Å molecular sieves before use. C
deoxygenated, distilled over sodium benzophenone, then
3
(Aldrich) was deoxygenated, distilled over CaH
2
, then
2
2
6 6
D
(Aldrich) was
2
2
ambient temperature and the reaction mixture was left to stir
stored over 3 Å molecular sieves before use. Ph
2
28
PBpin,
for 24 h. The solution was then dried in vacuo and washed
PBcat,8 Ph
d
PBMes
,
7b, 7c
t-Bu
8c
Ph
(
2
2
2
2 2
PBcat, Mes PBcat, and
with cold pentane (3 x 2 mL) to afford a yellow oil (t-Bu
3 mg, 92% isolated yield, t-Bu PBMes : 24 mg, 94% isolated
) δ: 8.25 (m, 2H, Ar), 7.13-7.05
ov m, 3H, Ar), 1.24 (d, JHP = 5.0 Hz, 9H, t-Bu), 1.22 (d, JHP = 5.0
2
PBcat:
η5-C
H
9 7
)Rh(η -coe)
2
25d
were prepared as previously reported.
2
2
2
2
NMR spectra were obtained on an Agilent DD2-500 MHz, a
Bruker AvanceIII-400 MHz, or a Varian Mercury-300 MHz
1
6 6
yield). H NMR (500 MHz, C D
(
1
13
1
31
1
11
1
spectrometer where H, C{ H}, P{ H}, and B{ H} NMR
chemical shifts (δ/ppm) are referenced to Me Si, Me Si, H PO
and BF ∙OEt , respectively. NMR spectra were also recorded
13
1
Hz, 9H, t-Bu); C{ H} NMR (125 MHz, C
6 6
D ) δ: 218.2 (d, JCP
=
4
4
3
4
,
4
=
1
C
0 Hz), 144.2 (d, JCP = 35 Hz), 133.1 (d, JCP = 2 Hz), 129.1 (d, JCP
3
2
13 Hz), 128.6 (d, JCP = 2 Hz), 33.4 (d, JCP = 22 Hz), 30.5 (d, JCP
=
1
11
on a JEOL JNM-GSX400 FT NMR ( H: 400 MHz; B: 128 MHz;
C: 100 MHz; P: 162 MHz) spectrometer. Chemical shifts (δ)
31
1
6 6
3 Hz); P{ H} NMR (162 MHz, C D ) δ: 39.5. Anal. calcd. for
1
3
31
-1
15
H23OP (250.32 g∙mol ): C, 71.97; H, 9.26. Found: C, 71.98;
1
are reported in ppm [relative to residual solvent peaks ( H and
H, 9.26.
1
3
11
31
3 2 3 4
C) or external F B·OEt ( B) and H PO ( P)]. Multiplicities
are reported as singlet (s), doublet (d), triplet (t), quartet (q),
quintet (quint), multiplet (m), broad (br), and overlapping (ov)
with coupling constants (J) reported in Hertz. Melting points
Synthesis of n-pentylC(O)PPh
chloride (100 mg, 0.74 mmol) and Ph
mmol) in toluene (5 mL) was stirred for 4 hours at RT.
2
(1d). A mixture of hexanoyl
PBpin (232 mg, 0.74
2
4
| Dalton Trans., 2019, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
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Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
Journal Name
ARTICLE
Removal of solvent and ClBpin in vacuo afforded 1d as a 136.2 (dt, JCP = 34 Hz, 12 Hz), 134.2 (t, JCP = 5 Hz), 133.4 (t, JCP
=
View Article Online
DOI: 10.1039/D0DT00579G
1
colourless oil. Yield: 198 mg (94%). H NMR (400 MHz, C
6 6
D )
6 Hz), 129.6, 129.1, 127.9 (dt, JCP = 6 Hz, 4 Hz), 127.0 (t, JCP = 7
δ: 7.45 (m, 4H, Ar), 7.04-6.99 (ov m, 6H, Ar), 2.33 (td, JHH = 7.3 Hz), 126.8, 126.0 (d, JCP = 1 Hz), 121.8, 111.6, 88.5 (t, JCP = 43
3
1
1
Hz, JHP = 3.2 Hz, 2H, C(O)CH
C(O)CH CH ), 1.05-0.88 (ov m, 4H, 2 × CH
Hz, 3H, CH
Hz), 134.8 (d, JCP = 18 Hz), 133.3 (d, JCP = 8 Hz), 129.3, 128.6 (d,
2
), 1.46 (quint, JHH = 7.3 Hz, 2H, Hz); P{ H} NMR (162 MHz, CDCl
3
) δ: 12.3. Anal. calcd. for
(594.38 g∙mol ): C, 74.77; H, 4.92. Found: C,
6 6
); C{ H} NMR (100 MHz, C D ) δ: 221.4 (d, JCP = 41 74.93; H, 4.88.
-1
2
2
2
), 0.67 (t, JHH = 7.3
37 3 2
C H29BO P
1
3
1
3
J
1
C
CP = 8 Hz), 45.3 (d, JCP = 45 Hz), 31.2, 24.0 (d, JCP = 4 Hz), 22.4, Synthesis of n-pentylC(OBpin)(PPh
2
)
2
(2d). A mixture of
3.8; 31P{ H} NMR (162 MHz, C
1
D
) δ: 16.0. Anal. calcd. for hexanoyl chloride (100 mg, 0.74 mmol) and Ph
6
6
2
PBpin (487 mg,
-1
o
18
H
21OP (284.33 g∙mol ): C, 76.04; H, 7.44. Found: C, 75.55; 1.56 mmol) in toluene (3 mL) was heated at 110 C for 5 days.
H, 7.40.
Removal of solvent and ClBpin in vacuo afforded a pale yellow
oil which was dissolved in 5 mL of hexane and stored at -30 C.
°
Synthesis of HCCCH
2
OC(O)PPh
2
(1e). To a stirred toluene (1 The resulting precipitate was collected by suction filtration to
°
mL) solution of propargyl chloroformate (25 mg, 0.21 mmol) afford 2d as a white solid. Yield: 308 mg (69%); mp 106-109 C.
was added a toluene (1 mL) solution of Ph
1
2
PBpin (66 mg, 0.21
3
H NMR (400 MHz, CDCl ) δ: 7.71 (m, 4H, Ar), 7.59 (m, 4H, Ar),
mmol). The reaction was allowed to proceed for 18 h at RT at 7.30-7.24 (ov m, 6H, Ar), 7.12 (t, JHH = 7.8 Hz, 2H, Ar), 7.04 (t,
which point the solvent and ClBpin were removed in vacuo to
afford 1e as a colourless oil. Yield: 54 mg (95%). H NMR (400 C(OBpin)CH
J
HH = 7.3 Hz, 4H, Ar), 2.04 (td, JHH = 7.3 Hz, JHP = 3.7 Hz, 2H,
), 1.57 (quint, JHH = 7.6 Hz, 2H, C(O)CH CH ), 1.11-
& pin), 0.89 (quint, JHH = 7.6 Hz, 2H, CH ),
) δ: 20
) δ: 136.0 (t, JCP = 13 Hz),
1
2
2
2
MHz, C
HH = 2.3 Hz, 2H, CH
NMR (100 MHz, C
6
D
6
) δ: 7.46 (m, 4H, Ar), 7.01-6.97(ov m, 6H, Ar), 4.27 (d, 1.04 (ov m, 14H, CH
2
2
1
3
1
11
J
2
), 1.83 (t, JHH = 2.3 Hz, 1H, C≡CH); C{ H} 0.71 (t, JHH = 7.6 Hz, 3H, CH
3
); B NMR (128 MHz, CDCl
3
1
3
1
6 6
D ) δ: 178.0 (d, JCP = 18 Hz), 134.6, (d, JCP
=
(br); C{ H} NMR (100 MHz, CDCl
3
1
7
9 Hz), 132.6 (d, JCP = 7 Hz), 129.5, 128.6 (d, JCP = 8 Hz), 77.6, 135.9 (t, JCP = 13 Hz), 135.5 (t, JCP = 3 Hz), 134.7 (t, JCP = 6 Hz),
4.9, 51.8; 31P{ H} NMR (162 MHz, C
1
D
) δ: -2.1. Anal. calcd. 129.0, 128.7, 128.0 (t, JCP = 4 Hz), 127.6 (t, JCP = 4 Hz), 86.3 (t,
CP = 36 Hz), 82.1, 38.1 (t, JCP = 8 Hz), 32.3, 25.8 (t, JCP = 13 Hz),
6
6
-1
for C16
7
H
13
O
2
P (268.25 g∙mol ): C, 71.64; H, 4.88. Found: C,
J
3
1
1
1.18; H, 4.96.
24.5, 22.4, 14.0; P{ H} NMR (162 MHz, CDCl
3
) δ: 11.2. Anal.
-1
calcd. for C36
2 2
) (2a). A mixture of benzoyl Found: C, 72.76; H, 7.31.
H43BO P (596.48 g∙mol ): C, 72.49; H, 7.27.
3 2
Synthesis of PhC(OBpin)(PPh
chloride (100 mg, 0.71 mmol) and Ph
mmol) in toluene (3 mL) was heated at 110 C for 5 days. Synthesis of Ph
2
PBpin (466 mg, 1.49
°
2
PCH(Ph)CH=C(OBpin)PPh
2
(2f). To a stirred CH
2
Cl
2
Removal of solvent and ClBpin in vacuo afforded an oily yellow (2 mL) solution of trans-cinnamoyl chloride (40 mg, 0.24 mmol) was
solid which was triturated with 5 mL of hexane. The resulting added a CH Cl (2 mL) solution of Ph PBpin (150 mg, 0.48 mmol).
2
2
2
solid was collected by suction filtration to afford 2a as a white The reaction was allowed to proceed for 18 h at 25°C at which point
°
1
solid. Yield: 328 mg (77%); mp 126-128 C. H NMR (400 MHz,
solvent was removed under vacuum to afford a waxy colourless
solid. The mixture was dissolved in hexane (20 mL) and stored at -
3
C D
6 6
) δ: 7.92 (m, 4H, Ar), 7.65 (m, 4H, Ar), 7.31 (d, JHH = 7.8 Hz,
H, Ar), 7.04-6.94 (ov m, 7H, Ar), 6.89-6.85 (ov m, 6H, Ar), 6.81
t, JHH = 7.3 Hz, 1H, Ar), 6.70 (t, JHH = 7.3 Hz, 1H, Ar), 0.70 (s,
2
0°C. Pale yellow crystals formed and were collected by suction
(
1
filtration to afford 2f as a pale yellow solid. Yield: 62 mg (41%); mp
2H, pin); 11B NMR (128 MHz, C
) δ: 141.2 (t, JCP = 3 Hz), 136.9, (ov dd, JCP = 13,
2 Hz), 136.4 (ov dd, JCP = 7, 6 Hz), 135.7 (ov dd, JCP = 13, 12
D
6 6
) δ: 20 (br); C{ H} NMR
13
1
07-112 C. 1H NMR (400 MHz, C
H, Ar), 7.29 (m, 4H, Ar), 7.12-7.10 (ov m, 2H, Ar), 7.06-7.04 (ov m,
H, Ar), 6.97-6.89 (ov m, 12H, Ar), 5.99 (d ov dd, JHH = 10.5 Hz, JHP
°
1
2
3
6
6 6
D
) δ: 7.63 (m, 2H, Ar), 7.39 (m,
6 6
(100 MHz, C D
1
=
Hz), 135.5 (ov dd, JCP = 5, 4 Hz), 128.9, 128.4, 127.9 (ov dd, JCP
, 3 Hz), 127.7 (ov dd, JCP = 5, 4 Hz), 127.5 (ov dd, JCP = 7, 6 Hz),
26.5, 125.6, 87.0 (t, JCP = 43 Hz), 82.3, 24.3; P{ H} NMR (162
=
.9, 6.9 Hz, 1H, HC=), 4.96 (dd, JHH = 10.5 Hz, JHP = 2.8 Hz, 1H,
4
1
HCPPh
2
), 0.80 (s, 6H, pin), 0.74 (s, 6H, pin); 11B NMR (128 MHz,
3
1
1
C
D
6 6
) δ: 21 (br); 13C{ H} NMR (100 MHz, C
1
6 6
D ) δ: 150.6 (dd, JCP = 20,
MHz, C
6 6
D ) δ: 15.0. Anal. calcd. for C37
H37BO
3
P
2
(602.45 g∙mol-
1
9 Hz), 140.6 (d, JCP = 10 Hz), 137.6 (d, JCP = 18 Hz), 136.4 (d, JCP = 11
Hz), 135.8 (d, JCP = 11 Hz), 135.5 (d, JCP = 18 Hz), 134.9 (d, JCP = 20
Hz), 134.6 (d, JCP = 20 Hz), 133.7 (d, JCP = 19 Hz), 133.3 (d, JCP = 17
Hz), 129.2, 129.1, 129.0, 128.6, 128.4, 128.3, 128.2, 128.1, 128.0,
)
: C, 73.77; H, 6.19. Found: C, 73.53; H, 6.24.
Synthesis of PhC(OBcat)(PPh
of Ph PBcat (61 mg, 0.2 mmol) was prepared in CH
A solution of benzoyl chloride (14 mg, 0.1 mmol) in CH
2
)
2
(2b). In a 20 mL vial, a solution
Cl (3 mL).
Cl (3
2
2
2
1
27.9, 127.7 (dd, JCP = 34, 13 Hz), 126.0 (d, JCP = 2 Hz), 82.9, 43.0
2
2
mL) was added at ambient temperature and the reaction (dd, JCP = 17, 8 Hz), 24.4, 24.0; 31P{ H} NMR (162 MHz, C
1
D
6 6
) δ: 7.2, -
-1
mixture was left to stir for 24 h. The solution was then dried in 1.1. Anal. calcd. for C39
3 2
H39BO P (628.48 g∙mol ): C, 74.53; H, 6.25.
vacuo, recrystallized by layering with pentane and CH Cl
2
2
,
Found: C, 74.76; H, 6.34.
decanted and washed with cold pentane (3 x 2 mL) to afford a
°
5
colourless crystalline solid. Yield: 54 mg (90%); mp 143-145 C. Synthesis of (η -C
9
H
7
)Rh(PhC(OBpin)(PPh
2
2
)
2
) (3a). To a stirred
)Rh(η -coe) (100 mg, 0.23
toluene (2 mL) solution of
(136 mg, 0.23 mmol). The reaction was
1
5
H NMR (500 MHz, CDCl
3
) δ: 7.63 (m, 4H, Ar), 7.55 (m, 4H, Ar), toluene (3 mL) solution of (η -C
H
9 7
2
7
(
1
.24-7.07 (ov m, 14H, Ar), 7.01-6.95 (ov m, 3H, Ar), 6.90-6.78 mmol) was added
a
1
1
1
ov m, 4H, cat); B{ H} NMR (128 MHz, CDCl
3
) δ: 21 (br); PhC(OBpin)(PPh
2
)
2
3
1
o
C{ H} NMR (125 MHz, CDCl
3
) δ: 147.7, 139.8 (t, JCP = 3 Hz), heated at 100 C for 6 h at which point the volume of solvent
This journal is © The Royal Society of Chemistry 20xx
Dalton Trans, 2019, 00, 1-3 | 5
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Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
Page 6 of 8
ARTICLE
Journal Name
o°
was halved in vacuo and the solution stored at -30 C.
A
potential of such addition products in FLP chemistry. The
View Article Online
DOI: 10.1039/D0DT00579G
precipitate was collected by suction filtration and washed with results of these studies will be reported in due course.
5
cold
toluene
(2
×
1
mL)
to
afford
(η -
C
9
H
7
)Rh(PhC(OBpin)(PPh
2
)
2
) as an orange solid. Yield: 90 mg
°
1
Conflicts of interest
There are no conflicts to declare.
(48%); mp 171-173 C. H NMR (400 MHz, C
6 6
D
) δ: 7.92 (m, 4H,
nd
Ar), 7.66 (m, 4H, Ar), 7.39 (m, 2H, Ar), 7.24 (2 order m, 2H,
IND), 7.03 (2 order m, 2H, IND), 6.99 (ov dd, JHH = 7.3 Hz, 4H,
nd
Ar), 6.93-6.86 (ov m, 7H, Ar), 6.55 (br m, 4H, Ar), 6.24 (ov td,
J
(
(
1
1
1
HH = JHRh = 2.8 Hz, 1H, IND), 5.86 (d, JHH = 2.8 Hz, 2H, IND), 0.72 Acknowledgements
11 13 1
s, 12H, pin); B NMR (128 MHz, C
100 MHz, C ) δ: 137.7 (t, JCP = 4 Hz), 135.9 (t, JCP = 16 Hz),
35.4 (t, JCP = 7 Hz), 135.3, (t, JCP = 8 Hz), 134.6 (t, JCP = 15 Hz),
6 6
D ) δ: 20 (br); C{ H} NMR
MCM thanks MtA for an ISRG award. CLBM, DWS and SAW are
grateful to the Natural Science and Engineering Research
Council (NSERC) of Canada for funding and DWS and SAW also
acknowledge support from the NSERC CRC program. DWS is
also grateful for the award of the JC Polanyi Award from
NSERC of Canada. Mount Allison University, the University of
Toronto and Carleton University are acknowledged for support
and Dan B.M. Durant is thanked for his expert technical
assistance. We also thank anonymous reviewers for very
helpful and constructive comments.
6 6
D
29.0, 128.8, 128.0, 127.0 (t, JCP = 5 Hz), 126.9 (t, JCP = 5 Hz),
26.1 (br s, 2C), 120.7, 118.6, 114.4, 105.7 (t, JCP = 17 Hz), 93.2
(
d, JCRh = 5 Hz), 82.8, 71.6 (td, JCP = 8 Hz, JCRh = 3 Hz), 24.2;
3
1
1
P{ H} NMR (162 MHz, C
6 6
D ) δ: 44.0 (d, JPRh = 198.1 Hz). Anal.
-1
calcd. for C46 Rh (820.50 g∙mol ): C, 67.34; H, 5.41.
Found: C, 67.96; H, 5.36.
3 2
H44BO P
X-Ray Diffraction Studies Single crystals of 1b and 2b were
2 2
grown from CH Cl solutions layered with pentane while
crystals of 2f and 3a were grown from saturated hexane or
toluene solutions, respectively. The crystals were coated with
paratone oil, mounted on a cryoloop and frozen under a
stream of cold nitrogen. Data were collected on a Bruker
Apex2 X-ray diffractometer (1b, 2b, and 2f) or a Bruker Photon
Notes and references
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Conclusions
2
1
Herein we have described the reactivity of
phosphinoboronate esters Ph PBpin and Ph PBcat, as well as
2 2
other phosphinoboron species, with various acyl chlorides to
give acyl phosphines with the by-product boron-chloride. In
addition, in several cases, reactions with a second equivalent
of phosphinoboron results in addition to the C=O double bond
1
2. J. H. W. LaFortune, A. Trofimova, H. Cummings, S. A. Westcott and D. W.
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2
)(PR’
2 2
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5
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| Dalton Trans., 2019, 00, 1-3
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