Pd-catalyzed carbonylative access to aroyl phosphonates from (hetero)aryl bromides

Article abstract of DOI:10.1039/c5cc02085a

The first transition-metal catalysed carbonylation with a phosphorus nucleophile is presented. This transformation provides efficient and mild access to aroylphosphonates under mild conditions, thus ensuring a broad substrate scope. The utility of aroylph

Full text of DOI:10.1039/c5cc02085a

View Article Online
View Journal
ChemComm
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: T. Skrydstrup, Z.
Lian, H. Yin and S. Friis, Chem. Commun., 2015, DOI: 10.1039/C5CC02085A.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/chemcomm

Page 1 of 5
ChemComm
Dynamic Article Links►
View Article Online
DOI: 10.1039/C5CC02085A
Cite this: DOI: 10.1039/c0xx00000x
www.rsc.org/xxxxxx
ARTICLE TYPE
Pd-Catalyzed Carbonylative Access to AroylPhosphonates
from(Hetero)Aryl Bromides
ZhongLian, Hongfei Yin, Stig D. Friis and Troels Skrydstrup*
Received (in XXX, XXX) XthXXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
The first transition-metal catalysed carbonylation with
a
phosphorus nucleophile is presented. This transformation
provides efficient and mild access to aroylphosphonates under
mild conditions, thus ensuring a broad substrate scope. The
10 utility of aroylphosphonates as useful reagents, capable of
participating in a number of transformations, is subsequently
demonstrated. Furthermore, access to [13C]-carbonyl labelled
aroylphosphonates is easily realised for the first time, as only a
near stoichiometric amount of CO is required applying this
15 carbonylation.
50
Scheme 1.Carbonylative couplings employing different nucleophiles.
Introduction
corresponding diorganophosphites and display both P- and O-
nucheophilicity.1,13 Initiating our search for suitable conditions,
which would ensure a satisfactory level of P- versus O-selectivity
The formation of new carbon-phosphorus bonds has traditionally
been undertaken via simple substitution reactions on carbon
fragments possessing an appropriate leaving group.1 Lately, a
20 number of transformations applying transition metal catalysis
have been presented as viable alternatives.2m These operate under
milder conditions, include alternative substrates, and provide easy
access to a wide range of phosphorus-containing products,2 which
are of increasing interest in both material science and biological
25 chemistry.1,3
In contrast to the preparation of aryl phosphonates via
transition metal catalysis, and despite the well-documented
usefulness of aroylphosphonates, their preparation has only been
undertaken through acyl substitution of acid chlorides with alkyl
30 phosphite reagents (Michaelis-Arbuzov-type reaction).4 However,
potential disadvantages associated with this approach includes
poor functional group tolerance associated with acid chloride
synthesis, their high reactivity, and the need for the carbonyl
group to already be installed in the starting material. A Pd-
35 catalysed carbonylative strategy would have the potential to
target these short comings. To this end, we set out to include
phosphorus among the competent nucleophiles in carbonylation
couplings, which are currently based on the following elements,
H,5 C,6 N,7 O,8 F,9 Si,10 S,11 and Cl12 (Scheme 1).
55 in this carbonylative cross coupling, we subjected equimolar
amounts of aryl bromide 1a and diethyl phosphite (2a) to carbon
monoxide (1.5 equiv), triethylamine (1.5 equiv), Pd(dba)2 (5
mol%) and XantPhos (5 mol%) in dioxane at 80 °C for 16 hours
(Table 1, entry 1).14 This ensured full conversion of the aryl
60 bromide and a 75% NMR yield of the desired product 3a with the
corresponding carboxylic acid as the main side-product. Although
various palladium sources proved effective for this carbonylation
(entries 2–6), Pd(dba)2 remained the ideal palladium source.
Applying a selection of mono- and bidentate phosphine ligands,
65 we observed a significant superiority of XantPhos-type ligands
(entries 7–12).15 Employing more sterically encumbered bases
(Cy2NMe or DIPEA) only served to reduce reaction efficiency
(entries 13 and 14), while using the stronger base DBU resulted
in O-acylation, ultimately leading to the corresponding carboxylic
70 acid (entry 15). Finally, increasing the temperature to 90 °C and
employing a 0.5 equivalent excess of 1a boosted the NMR yield
to 87% (entry 17).
Having developed suitable reaction conditions for this
carbonylative preparation of aroylphosphonates, we next turned
75 our attention towards the substrate scope of this C–P bond
forming transformation (Scheme 2). Product 3a resulting from
the coupling of the electron rich 4-bromoanisole (1a) was isolated
in 79% yield. In comparison with the observed 86% NMR yield,
slight decomposition of 3a had occurred during purification
80 possibly via hydrolysis to 4-methoxylbenzoic acid.16 The
methoxy-group in the meta-position also provided the product in
a good isolated yield of 3b. Other electron donating substituents
such as methyl, tert-butyl and dimethylamino were also tolerated
under the optimised reaction conditions, thus providing products
40
With the aim of developing a carbonylative route for the
preparation of aroylphosphonates with the generation of two new
bonds, one of these being a C–P bond, we settled on H-
phosphonates as nucleophiles. These air stable, easy to handle,
and inexpensive P(V)-reagents are in equilibrium with their
45
Carbon Dioxide Activation Centre (CADIAC), Interdisciplinary Nano science Center
(iNANO) and Department of Chemistry, Aarhus University, Gustav Wieds Vej 14, 8000
Aarhus C, Denmark. E-mail: ts@chem.au.dk; www.skrydstrup-group.com
†
Electronic Supplementary Information (ESI) available. See DOI: 10.1039/b000000x/
This journalis© The Royal Society of Chemistry [year]
[journal], [year], [vol], 00–00 |1

ChemComm
Page 2 of 5
CO (1.5 equiv)
Pd(dba)2 (5 mol%)
XantPhos (5 mol%)
Et3N (1.5 equiv)
Table 1. Optimisation of Pd-catalysed carbonylative aroylphosphonate
synthesis with selected examples.
O
O
P
OEt
OR
OR
(Het)Ar
P
O
(Het)Ar Br
+
1.5 equiv CO
'Pd' (5 mol%)
View Article Online
OEt
H
Br
O
P
O
OEt
OEt
DOI: 10.1039/C5CC02085A
OEt
OEt
Dioxane (0.1 M), 70 oC–90 oC, 16 h
P
3
1
2
Phosphine (10 mol%)
Base (1.5 equiv)
Dioxane (0.1 M), 80 οC, 16 h
+
H
O
O
O
O
MeO
(1.0 equiv)
MeO
2
1a
3a
MeO
OEt
OEt
OEt
OEt
OEt
OEt
P
(1.0 equiv)
P
P
O
Yielda(%)
O
O
Entry
1
[Pd]-catalyst
Pd(dba)2
Ligand
XantPhos
XantPhos
XantPhos
XantPhos
XantPhos
XantPhos
PPh3
Base
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
MeO
t-Bu
3a, 79%a
3b, 73%b
O
3c, 80%a
O
75
40
60
47
53
55
0
O
2
[Pd(cinnamyl)Cl]2
PdCl2
OEt
OEt
OEt
OEt
P
P
P
3
OEt
OEt
O
O
O
N
MeO
Cl
4
Pd(PPh3)2Cl2
Pd(COD)Cl2
Pd(OAc)2
Pd(dba)2
3d, 69%a
3e, 92%a
O
3f, 88%a
O
OMe
5
O
6
OEt
OEt
OEt
OEt
OEt
P
P
P
7
OEt
O
O
3h, 61%c
O
O
8
Pd(dba)2
(tBu)3P•HBF4
CataCXium A
XPhos
0
F
3g, 75%b
3i, 62%c
9
Pd(dba)2
0
O
O
O
10
11
12
13
14
15
16b
17b,c
Pd(dba)2
0
OEt
OEt
OEt
OEt
P
P
P
Pd(dba)2
DPEPhos
NiXantPhos
34
58
44
34
0
OEt
OEt
O
O
O
Pd(dba)2
Ph
3j, 77%c
68% from OTfc
3k, 50%c
3l, 76%b
Pd(dba)2
XantPhos
XantPhos
XantPhos
XantPhos
XantPhos
Cy2NMe
DIPEA
DBU
Pd(dba)2
O
O
O
Pd(dba)2
OEt
P
OEt
OEt
OEt
P
P
Pd(dba)2
Et3N
83
87
OEt
O
OEt
O
O
N
O
Pd(dba)2
Et3N
3m, 67%b
3n, 51%a
3o, 60%a
a 1H-NMR yield using internal standard (1,3,5-trimethoxybenzene).
O
O
OEt
OEt
OEt
OEt
5
b90 °C. c 1.5 equiv of (Het)Ar-Br.
P
P
O
O
S
S
3q, 41%a
3p, 58%b
3c, 3d and 3e in isolated yields of 80%, 69% and 92%,
respectively. Likewise, the disubstituted 3f was obtained from 4-
bromoveratrole in an 88% yield after flash column
chromatography.
The use of bromobenzene led to better P- versus O-selectivity
at a slightly lower reaction temperature of 80 °C, resulting in a
75% isolated yield of 3g. Tolerance towards other halides on the
aryl-ring was demonstrated by the synthesis and isolation of
compounds 3h and 3i in yields of 61% and 62%, respectively.
O
O
O
O
O
P
O
P
O
O
MeO
MeO
3s, 88%a
3r, 80%a
40
10
Scheme 2. Scope of the carbonylative aroylphosphonate synthesis. For
reaction conditions, see supporting information and yields are calculated
from the amount of H-phosphonate.a 90 °C. b 80 °C. c 70 °C.
As this new carbonylative transformation only requires a
15 The reduced stability of these more electron poor products, which
are prepared at 70 °C, is highlighted by the corresponding 75%
and 78% NMR yields of 3h and 3i, respectively. Coupling of 4-
bromobiphenyl was most efficient at 70 °C and gave product 3j
in a satisfactory yield of 77%, while the corresponding aryl
45 slight excess of CO generated from 1.5 equivalents of COgen, the
methodology is adaptable to isotope labelling.14 Simply applying
13COgen instead of COgen, allowed products [13C]-3a and [13C]-
3e to be prepared in good yields after subjection to the optimised
reaction conditions (Scheme 3).17
20 triflate produced the product in
a slightly lower yield.
50
Having established a mild and efficient Pd-catalysed
Aroylphosphonate 3k displaying a ketone was, despite the
electrophilic nature of this functionality, isolated in a 50% yield
with no detection of side-products involving this ketone.
Bromonaphthalenes also proved to be competent substrates for
25 this transformation, providing 3l and 3m in 76% and 67% yield,
respectively.
carbonylative strategy for the synthesis of aroylphosphonates, we
set out to underline the utility of these products (Scheme 4). α-
Fluorination was easily effected in a 55% yield by treating
benzoylphosphonate 3g with DAST.18 Tertiary alcohol 5 was
55 easily assembled in an excellent yield by using acetone as the
nucleophile under enamine-catalysis.19
Shifting focus towards heteroaryl bromides, N-methyl
protected 5-bromoindole was transformed into aroylphosphonate
3n in
a 51% isolated yield, while a 60% yield of the
30 benzofuranderivative 3o could be secured. Bromothiophene
displaying substrates also underwent successful coupling to
afford 3p and 3q in 58% and 41% isolated yield, respectively.
Next, we turned our attention to the other H-phosphonate
nucleophiles. Under the optimised reaction conditions, 1a readily
35 reacts with both di-n-butyl phosphite, as well as the more
sterically encumbered diisopropylphosphite, thus furnishing
aroylphosphonates 3r and 3s in yields of 80% and 88%,
respectively. Unfortunately, diarylphosphites were not suitable
substrates for this chemistry.
Scheme 3. 13C-Labelling of aroylphosphonates using 13COgen.
2|Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]

Page 3 of 5
ChemComm
35
In summary, we have presented the first transition metal-
catalysed carbonylation employing phosphorus-based
a
View Article Online
nucleophile. This novel methodology provides easy, safe and
DOI: 10.1039/C5CC02085A
high yielding access to a selection of aroylphosphonates under
mild reaction conditions, thus allowing for a broad substrate
40 scope. The effectiveness of this transformation, even under a near
stoichiometric amount of carbon monoxide, also allows for
isotopic acyl labelling, as demonstrated herein by the
incorporation of 13CO. Consequently, we believe this
methodology provides an attractive alternative to the classically
45 employed acyl substitution of acid chlorides.
The financial support from the Danish National Research
Foundation, (grant no. DNRF118), the Villum Foundation, the
Danish Council for Independent Research: Technology and
Production Sciences, the Lundbeck Foundation, the Carlsberg
50 Foundation, Aarhus University and the Chinese Scholarship
Council (grants to Z. L. and H. Y.) are greatly appreciated.
Scheme 4. Utilisation of the aroylphosphonate products. Reaction
conditions: (a) DAST (4.0 equiv), 0 °C to r. t. (b) L-proline (0.5 equiv),
acetone, rt, 24 h.(c) NH2NMe2 (1.4 equiv), AcOH, rt, 2 h. (d) PhCHO (1.1
5 equiv), KCN (0.3 equiv), DMF, rt, 6 h. (e) PMe3 (1.0 equiv), THF, rt, 2 h.
Hydrazine also proved reactive towards 3g, producing the
hydrazone derivative 6 in good yield.20 Aroylphosphonates can
be converted into aroyl nucleophiles by treatment with cyanide,
and after phosphonate-phosphate rearrangement, the formed
10 carbanion can be trapped to form for example cross-benzoin
products like 7.21 Furthermore, the carbonyl group of
aroylphosphonates can be chemoselectively reduced under mild
conditions by treatment with PMe3, thus affording benzylic
alcohols like 8.22
Notes and references
1
(a) Engel, R. Handbook of Organophosphorus Chemistry; Marcel Dekker:
New York, 1992. (b) The Chemistry of Organophosphorus Compounds,
Hartley, F. R., Ed.; Wiley: New York, 1996; Vol. 4. (c) Quin, L. D. A
Guide to Organophosphorus Chemistry; Wiley: New York, 2000.
55
60
65
70
15
Finally, a plausible mechanism for this Pd-catalyzed
2
(a) O. Berger, C. Petit, E. L. Deal and J. L. Montchamp, Adv. Synth.
Catal., 2013, 355, 1361-1373. (b) B. Q. Xiong, M. Li, Y. X. Liu, Y. B.
Zhou, C. Q. Zhao, M. Goto, S. F. Yin and L. B. Han, Adv. Synth. Catal.,
2014, 356, 781-794. (c) K. Xu, F. Yang, G. D. Zhang and Y. J. Wu,
Green Chem., 2013, 15, 1055-1060. (d) A. J. Bloomfield and S. B. Herzon,
Org.Lett., 2012, 14, 4370-4373. (e) C. Huang, X. Tang, H. A. Fu, Y. Y.
Jiang and Y. F. Zhao, J. Org. Chem., 2006, 71, 5020-5022. (f) H. H. Rao,
Y. Jin, H. Fu, Y. Y. Jiang and Y. F. Zhao, Chem-Eur. J., 2006, 12, 3636-
3646. (g) Y. Matano, K. Matsumoto, Y. Terasaka, H. Hotta, Y. Araki, O.
Ito, M. Shiro, T. Sasamori, N. Tokitoh and H. Imahori, Chem.-Eur. J.,
2007, 13, 891-901. (h) N. T. McDougal, J. Streuff, H. Mukherjee, S. C.
Virgil and B. M. Stoltz, Tetrahedron Lett., 2010, 51, 5550-5554. (i) M.
Toffano, C. Dobrota and J. C. Fiaud, Eur. J. Org. Chem., 2006, 650-656.
(j) E. L. Deal, C. Petit and J. L. Montchamp, Org.Lett., 2011, 13, 3270-
3273. (k) M. Kalek, M. Jezowska and J. Stawinski, Adv. Synth.Catal.,
2009, 351, 3207-3216. For a review, see: (l) F. M. J. Tappe, V. T. Trepohl
and M. Oestreich, Synthesis, 2010, 3037-3062. (m) E. Jablonkai and G.
Keglevich, Curr. Org. Synth., 2014, 11, 429-453.
carbonylative approach towards aroylphosphonates is illustrated
in Figure 1. Initially, oxidative addition of palladium(0) into the
(hetero)aryl bromide (or triflate) bond, coordination of carbon
monoxide and migratory insertion affords the palladium-acyl
20 complex A. Diorgano H-phosphonates B are in equilibrium with
their corresponding diorganophosphites C, and coordination of
this P(III) reagent to palladium, affords either O-bound complex
D or P-bound complex E. These are like to be equilibrium as
demonstrated for enolates.23 Subsequent deprotonation of E with
25 the mild amine base used, would provide palladium(II) complex
F, which upon reductive elimination forms the desired product
while regenerating the ligated palladium(0). Observation of
carboxylic acid as the major side-product may be rationalised by
deprotonation of the O-bound complex D, followed by reductive
30 elimination to form G. Upon exposure to moisture, G is easily
hydrolysed into the corresponding benzoic acid.
75 3
(a) Corbridge, D. E. C. Phosphorus: An Outline of Its Chemistry,
Biochemistry and Uses, 5th ed.; Elsevier: Amsterdam, 1995. (b)
Aminophosphonic and Aminophosphinic Acids: Chemistry and
Biological Activity; Kukhar, V. P., Hudson, H. R., Eds.; Wiley:
Chichester, 2000. (c) E. Soulier, J. C. Clement, J. J. Yaouanc and H. des
Abbayes, Tetrahedron Lett., 1998, 39, 4291-4294. (d) L. Devel, V.
Rogakos, A. David, A. Makaritis, F. Beau, P. Cuniasse, A. Yiotakis and V.
Dive, J. Biol. Chem., 2006, 281, 11152-11160. (e) F. R. Alexandre, A.
Amador, S. Bot, C. Caillet, T. Convard, J. Jakubik, C. Musiu, B. Poddesu,
L. Vargiu, M. Liuzzi, A. Roland, M. Seifer, D. Standring, R. Storer and C.
B. Dousson, J. Med. Chem., 2011, 54, 392-395.
O
Ar Br
80
OR
OR
Ar
P
PdL2
O
O
P
P
Ar
Br
P
P
Ar
OR
OR
Pd
Pd
Et3N HBr
85
P
O
OR
P
4
(a) M. Sekine, M. Satoh, H. Yamagata and T. Hata, J. Org. Chem., 1980,
45, 4162-4167. (b) Y. Huang, F. Berthiol, B. Stegink, M. M. Pollard and
A. J. Minnaard, Adv. Synth.Catal., 2009, 351, 1423-1430. (c) M. Sprecher
and D. Kost, J. Am. Chem. Soc., 1994, 116, 1016-1026.
O
F
CO
Hydrolysis
Ar
O
OR
Et3N HBr
Et3N
G
O
90 5
For selected examples of carbonylative C–H cross coupling: (a) H.
Neumann, R. Kadyrov, X. F. Wu and M. Beller, Chem.-Asian J., 2012, 7,
2213-2216. (b) W. Y. Hao, G. D. Ding and M. Z. Cai, Catal. Commun.,
2014, 51, 53-57. (c) S. Korsager, R. H. Taaning, A. T. Lindhardt and T.
Skrydstrup, J. Org. Chem., 2013, 78, 6112-6120. (d) J. W. Jiang, P. P.
Wang and M. Z. Cai, J. Chem. Res., 2014, 218-222.
Ar
OH
Et3N
O
O
Br
P
P
P
Ar
Ar
Pd
Pd
A
P
Br
P
OR
HO
Br
95
O
OR
6
For selected examples of carbonylative C–C cross coupling: (a) Z. H.
Zhang, Y. Y. Liu, M. X. Gong, X. K. Zhao, Y. Zhang and J. B. Wang,
Angew. Chem. Int. Edit., 2010, 49, 1139-1142. (b) A. Park and S. Lee,
Org. Lett., 2012, 14, 1118-1121. (c) Z. Lian, S. D. Friis and T.
Skrydstrup, Angew. Chem. Int. Ed., 2014, 53, 9582-9586. (d) K. T.
Neumann, S. R. Laursen, A. T. Lindhardt, B. Bang-Andersen and T.
Skrydstrup, Org. Lett., 2014, 16, 2216-2219. (e) K. M. Bjerglund, T.
Skrydstrup and G. A. Molander, Org. Lett., 2014, 16, 1888-1891. (f) S.
Korsager, D. U. Nielsen, R. H. Taaning and T. Skrydstrup, Angew. Chem.
P
P
OR
OR
Ar
P
E
Pd
C
B
HO P
P(III)
O
OR
H
O
D
OR
P
P(V)
100
RO
RO
H
Figure1. Proposed mechanism of carbonylative aroylphosphonate
synthesis.
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 |3

ChemComm
Page 4 of 5
Int. Edit., 2013, 52, 9763-9766. (g) Z. Lian, S. D. Friis and T. Skrydstrup,
Chem. Commun., 2015, 51, 1870-1873. (h) Z. Lian, S. D. Friis and T.
Skrydstrup, Chem. Commun., 2015, 51, 3600-3603.
View Article Online
7
For selected examples of carbonylative C–N cross coupling reaction: (a)
X. F. Wu, H. Neumann and M. Beller, Chem-Asian J., 2010, 5, 2168-
2172. (b) T. T. Dang, Y. H. Zhu, J. S. Y. Ngiam, S. C. Ghosh, A. Q. Chen
and A. M. Seayad, ACS Catal., 2013, 3, 1406-1410. (c) S. R. Borhade, A.
Sandstrom and P. I. Arvidsson, Org. Lett., 2013, 15, 1056-1059. (d) F.
Tinnis, O. Verho, K. P. J. Gustafson, C. W. Tai, J. E. Backvall and H.
Adolfsson, Chem.-Eur. J., 2014, 20, 5885-5889. (e) T. Fang, X. H. Gao,
R. Y. Tang, X. G. Zhang and C. L. Deng, Chem. Commun., 2014, 50,
14775-14777. (f) S. D. Friis, T. Skrydstrup and S. L. Buchwald, Org.
Lett., 2014, 16, 4296-4299. (g) Z. Lian, S. D. Friis, A. T. Lindhardt and T.
Skrydstrup, Synlett, 2014, 25, 1241-1245.
DOI: 10.1039/C5CC02085A
5
10
15 8
For selected examples of carbonylative C–O cross coupling reaction: (a)
W. Magerlein, A. F. Indolese and M. Beller, Angew. Chem. Int. Edit.,
2001, 40, 2856-2859. (b) C. M. Kormos and N. E. Leadbeater,
Org.Biomol. Chem., 2007, 5, 65-68. (c) Z. Xin, T. M. Gogsig, A. T.
Lindhardt and T. Skrydstrup, Org. Lett., 2012, 14, 284-287. (d) J.
Schranck, A. Tlili, H. Neumann, P. G. Alsabeh, M. Stradiotto and M.
Beller, Chem.-Eur. J., 2012, 18, 15592-15597. (e) H. Zhang, R. Y. Shi, A.
X. Ding, L. J. Lu, B. R. Chen and A. W. Lei, Angew. Chem. Int. Edit.,
2012, 51, 12542-12545.
20
9
(a) T. Sakakura, M. Chaisupakitsin, T. Hayashi and M. Tanaka, J.
Organomet. Chem., 1987, 334, 205-211. (b) T. Okano, N. Harada and J.
Kiji, Bull. Chem. Soc. Jpn., 1992, 65, 1741-1743.
25
10 X. F. Wu, H. Neumann and M. Beller, Tetrahedron Lett., 2012, 53, 582-
584.
11 (a) H. Cao, L. McNamee and H. Alper, J. Org. Chem., 2008, 73, 3530-
3534. (b) Y. H. Hu, J. Liu, Z. X. Lu, X. C. Luo, H. Zhang, Y. Lan and A.
W. Lei, J. Am. Chem. Soc., 2010, 132, 3153-3158. (c) M. N.
Burhardt, Ahlburg, A. and T. Skrydstrup, J. Org. Chem., 2014, 79,
11830–11840. (d) S. M. Islam, R. A. Molla, A. S. Roy and K. Ghosh, Rsc.
Adv., 2014, 4, 26181-26192.
30
35 12 J. S. Quesnel and B. A. Arndtsen, J. Am. Chem. Soc., 2013, 135, 16841-
16844.
13 A. De Blieck, K. G. R. Masschelein, F. Dhaene, E. Rozycka-Sokolowska,
B. Marciniak, J. Drabowicz and C. V. Stevens, Chem. Commun., 2010,
46, 258-260.
40 14 Carbon monoxide was delivered to the reaction by decarbonylative Pd-
catalysis of COgen (9-methyl-9H-fluorene-9-carbonyl) in the two-
chamber system COware, see: (a) P. Hermange, A. T. Lindhardt, R. H.
Taaning, K. Bjerglund, D. Lupp and T. Skrydstrup, J. Am. Chem. Soc.,
2011, 133, 6061-6071. For other CO releasing molecules in COware, see
45
(b) S. D. Friis, R. H. Taaning, A. T. Lindhardt and T. Skrydstrup, J. Am.
Chem. Soc., 2011, 133, 18114-18117. (c) P. Nordeman, L. R. Odell and
M. Larhed, J. Org. Chem., 2012, 77, 11393-11398. (d) L. R. Odell, F.
Russo and M. Larhed, Synlett, 2012, 23, 685-698.
15 (a) P. W. N. M. van Leeuwen, P. C. J. Kamer, J. N. H. Reek and P.
Dierkes, Chem. Rev., 2000, 100, 2741-2770. (b) J. R. Martinelli, D. A.
Watson, D. M. M. Freckmann, T. E. Barder and S. L. Buchwald, J. Org.
Chem., 2008, 73, 7102-7107.
50
16 S. M. A. Kedrowski and D. A. Dougherty, Org. Lett., 2010, 12, 3990-
3993.
55 17 In a similar matter, radioactive 14C-labeled aroylphosphonates would also
be easily accessible ascarbon-14 labelling using 14COgen has been
established using a setup equivalent to carbon-13 labelling. See: A. T.
Lindhardt, R. Simonssen, R. H. Taaning, T. M. Gøgsig, G. N. Nilsson, G.
Stenhagen, C. S. Elmore and T. Skrydstrup, J. Labelled Compd.
60
Radiopharm., 2012, 55, 411-418.
18 T. R. Burke, M. S. Smyth, A. Otaka and P. P. Roller, Tetrahedron Lett.,
1993, 34, 4125-4128.
19 S. Samanta and C. G. Zhao, J. Am. Chem. Soc., 2006, 128, 7442-7443.
20 Z. H. Kudzin and A. Kotynski, Synthesis, 1980, 1028-1032.
65 21 A. S. Demir, O. Reis, A. C. Igdir, I. Esiringu and S. Eymur, J. Org.
Chem., 2005, 70, 10584-10587.
22 W. Zhang and M. Shi, Chem. Commun., 2006, 1218-1220.
23 D. A. Culkin and J. F. Hartwig, Organometallics, 2004, 23, 3398-3416
70
4|Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]

Page 5 of 5
ChemComm
View Article Online
DOI: 10.1039/C5CC02085A
This first carbonylative coupling employing a phosphorus-
based nucleophile provides easy and safe access to acyl
phosphonates under mild conditions.
5
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 |5