Solvent-free Zn(OTf)2-catalyzed dehydrative cross coupling of propargyl alcohols with diarylphosphine oxides to afford allenylphosphine oxides

Article abstract of DOI:10.1080/10426507.2018.1490281

A less expensive and more environmentally friendly Zn(OTf)₂-catalyzed dehydrative coupling reaction of propargyl alcohols with diarylphosphine oxides is reported. The reaction takes place under mild and solvent free conditions, and features a h

Full text of DOI:10.1080/10426507.2018.1490281

Phosphorus, Sulfur, and Silicon and the Related Elements
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Solvent-free Zn(OTf)2-catalyzed dehydrative
cross coupling of propargyl alcohols with
diarylphosphine oxides to afford allenylphosphine
oxides
Jianlin Yang, Ming Zhang, Chao Dong, Li-Biao Han & Ruwei Shen
To cite this article: Jianlin Yang, Ming Zhang, Chao Dong, Li-Biao Han & Ruwei Shen
(2018): Solvent-free Zn(OTf)2-catalyzed dehydrative cross coupling of propargyl alcohols with
diarylphosphine oxides to afford allenylphosphine oxides, Phosphorus, Sulfur, and Silicon and the
Related Elements, DOI: 10.1080/10426507.2018.1490281
To link to this article: https://doi.org/10.1080/10426507.2018.1490281
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Phosphorus, Sulfur and Silicon, 193: xxxx-yyyy, 2018
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ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1800/10426507.2015
Solvent-free Zn(OTf)2-catalyzed dehydrative cross coupling of
propargyl alcohols with diarylphosphine oxides to afford
allenylphosphine oxides
†
†
Jianlin Yanga, , Ming Zhanga, , Chao Donga, Li-Biao Hanb, Ruwei Shena,*
aState Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing
Tech University, Nanjing 210009, China and bNational Institute of Advanced Industrial Science & Technology
(AIST), Tsukuba, Ibaraki, 305-8565, Japan
Abstract A less expensive and more environmentally friendly Zn(OTf)2-catalyzed dehydrative coupling reaction of propargyl
alcohols with diarylphosphine oxides is reported. The reaction takes place under mild and solvent free conditions, and features a
high regioselectivity to provide an effective method for the synthesis of some diarylphosphinyl allenes in moderate to high yields.
Keywords allenylphosphoryl compound; zinc catalysis; dehydrative coupling; solvent-free synthesis; regioselectivity
compounds.4 Furthermore, some of these
INTRODUCTION
compounds have also been applied in
cyclization reactions to access other
structurally advanced organophosphorus
compounds.5,6
Allenylphosphoryl
compounds
are
structurally interesting and have many
applications in organic synthesis due to the
presence of the unique allenic structure and
A classical method for the synthesis of
allenylphosphoryl compounds is the Horner-
Mark [2,3]-rearrangement reaction of
propargyl phosphates. This method was first
discovered in the 1960s by researchers from
industry (Scheme 1A).7 Although this
method is still frequently used today, it
suffers from low yields and limited scopes,
the
functionality.1-6 They can undergo selective
additions with nucleophiles and
versatile
organophosphorus
electrophiles to afford stereodefined
functionalized olefins.1-3 Particularly, the
catalytic asymmetric hydroarylation of
diphenylphosphinylallenes can produce
valuable
chiral
organophosphorus
Received xx yyyy 2018 accepted xx yyyy 2018
CONTACT: Ruwei Shen, State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech
University, Nanjing 210009, China; . Email: shenrw@njtech.edu.cn. †These authors contributed equally.

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and requires the use of highly toxic,
moisture-sensitive and odorous phosphorus
chlorides. These drawbacks stimulate the
search for new methods.8-14 In 2010,
Stawinski8 reported a Pd-catalyzed cross-
coupling reaction of propargylic chlorides
(carbonates) with the stable and readily
available P(O)H compounds to produce
allenylphosphonates and related compounds
based on the well-known Pd-catalyzed
propargylic substitution involving allenyl-
and propargyl-palladium intermediates
(Scheme 1B, eq. a). However, the use of
expensive palladium catalyst and bidentate
ligand (DPEPhos) limited its use. In 2016,
The direct dehydrative C-P coupling
reaction of propargyl alcohols with P(O)H
compounds represents the most advanced
method (Scheme 1C). The benefit of this
approach is evident since it employs readily
available and low-cost alcohols without
wasteful prefunctionalization and principally
produces water as the only byproduct.11
Very recently, the groups of Zhao12 and
Yang13 achieved such catalytic dehydrative
C-P couplings of some propargylic alcohols
with P(O)H compounds by using Cu(OTf)2
and AgOTf as the catalysts. Meanwhile, we
found that CdCl2 is an active catalyst
capable of promoting the dehydrative
coupling of several propargyl alcohols with
diarylphosphine oxides.14 Comparably, our
we reported
a
cheap Cu-catalyzed
propargylic substitution of propargylic
acetates with P(O)H compounds via
Cd-catalyzed
advantageous
system
for
is
particularly
alcohol
allenylidene intermediates
to
afford
propargyl
allenylphosphoryl compounds in high yields
(Scheme 1C, eq. b).9,10 Propargyl acetates
bearing very sterically hindering substituents
at the propargylic position and a variety of
substrates which bear sterically demanding
substituents at the triple bond terminus to
afford the allenyl products in high yields
most likely due to a distinct mechanism
involving the formation of propargyl
phosphate intermediates.14 However, the use
of the hazardous and non-environmental-
friendly cadmium catalyst becomes a major
concern when applying this method.15 As a
continued effort, herein we report our recent
P(O)H
compounds
including
H-
phosphonates,
H-phosphinates
and
diarylphosphine oxides all can be used for
the reaction, yet internal propargylic acetates
cannot be applied.
Received xx yyyy 2018 accepted xx yyyy 2018
CONTACT: Ruwei Shen, State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech
University, Nanjing 210009, China; . Email: shenrw@njtech.edu.cn. †These authors contributed equally.

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finding on an alternative Zn-catalyzed
reaction of propargyl alcohols with
diarylphosphine oxides. We find that
Zn(OTf)2 can be used as the catalyst for the
dehydrative coupling of propargyl alcohols
and diarylphosphine oxides to generate
allenylphosphine oxides under solvent free
conditions. Because the zinc catalyst is
much less toxic and cheaper, the reaction
catalyzed by this metal should be more
practically useful.
8). The use of other solvents such as toluene,
THF, dioxane, DMF and DMSO all gave
poor results (Table 2-6). When we
investigated the catalytic effect of the more
cationic Zn(OTf)2, we found that the
reaction performed in the presence of 10
mol% Zn(OTf)2 under solvent free
conditions afforded the product 3a in 92%
yield (Table 1, entry 10). However, the use
of a solvent has a negative impact on the
product yield of the reaction (Table 1,
entries 11-13). Even when the reaction was
performed in MeCN, which is a suitable
solvent for the ZnCl2-catalyzed reaction,
only a trace amount of the expected product
was detected (Table 1, entry 11). Although
the product yield was slightly improved
when 2 equiv of 1a was used (Table 1, entry
9), we noted that the use of a more amount
of the propargyl alcohol that could keep a
good state of stirring of the reaction mixture
benefited for the re-productivity of the
yields. The reaction of 1a and 2a in a 1/1
molar ratio sometimes gave a decreased
yield, because it became difficult to
maintain a good state of continuous stirring
due to the formation of a very slurry mixture
when the reaction proceeded. Thus we
finally defined the optimal conditions as
Scheme 1 The development of synthetic methods to
access allenylphosphoryl compounds
RESULTS AND DISCUSSION
We initially found that ZnCl2 was incapble
of catalyzing the C-P coupling of 3-tert-
butyl-1-phenylprop-2-yn-1-ol (1a) with
Ph2P(O)H (2a) in DCE to produce the
allenylphosphine oxide 3a (Table 1, entry
1). A close study reveals that the solvent
plays a significant role in the reaction
outcome. When MeCN was used as the
solvent, the allenyl product 3a was formed
in 73% yield (Table 1, entry 7). When the
reaction was performed under solvent free
conditions, the desired product 3a was also
formed, but in a lower yield (Table 1, entry
Received xx yyyy 2018 accepted xx yyyy 2018
CONTACT: Ruwei Shen, State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech
University, Nanjing 210009, China; . Email: shenrw@njtech.edu.cn. †These authors contributed equally.

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DOI: 10.1800/10426507.2015
follows: 1a/2a: 2/1, 10 mol% of Zn(OTf)2,
no solvent, 100 oC, 12 h.
11 and 12, the products 3k and 3l were
successfully prepared in good to high yields.
Probably due to a low reactivity, the reaction
of 1m catalyzed by Zn(OTf)2 only gave a
trace amount of the product. Under the
conditions using ZnCl2 as the catalyst, the
reaction could give rise to the product in 26%
yield (Table 2, entry 13). In addition, the
reactions of propargyl alcohols bearing a
phenyl group or cyclopropyl group at the
triple bond terminus also produce the
corresponding products in low yields (Table
2, entries 14 and 15).
Table 2 Optimization of the reaction conditions of
1a and 2aa
Table 2 shows the results of the
Zn(OTf)2-catalyzed C-P coupling reaction of
a variety of propargyl alcohols with
diphenylphosphine oxide (2a). In addition to
1a, propargyl alcohols 1b-1e bearing the t-
butyl group and electron-deficient phenyl
groups at the propargylic position reacted
smoothly with 2a affording the expected
products in high yields (Table 2, entries 2-5).
The reactions of propargyl alcohols 1g-1i
bearing the n-butyl group at the triple bond
terminus also react well with 2a to afford the
corresponding products 3g-3i in good yields
(Table 2, entries 7-9). However, the reaction
of the propargyl alcohol 1f or 1j that bears
an electron-rich phenyl group at the
propargylic position took place with poor
selectivity. The reactions mainly gave the
propargyl diphenylphosphine oxides as the
major products (Table 2, entries 6 and 10).
The reaction can also be applied to
propargyl alcohols with two aryl groups at
Table 2 Zn(OTf)2-catalyzed C-P coupling of
propargylic alcohols 1 with diarylphosphine oxide
2aa
We also examined the reactions of other
substituted diarylphosphine oxides. As
shown in Table 3, typical diarylphosphine
oxides which bear electron-donating and
electron-withdrawing substituents on the
phenyl rings are all good substrates to give
rise to the expected products 3p-3s in high
yields. The reactions of substrates bearing
different aryl groups also took place
smoothly to give the corresponding products
3t and 3u in high yields. Since
the propargylic position. As shown in entries
Received xx yyyy 2018 accepted xx yyyy 2018
CONTACT: Ruwei Shen, State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech
University, Nanjing 210009, China; . Email: shenrw@njtech.edu.cn. †These authors contributed equally.

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diarylphosphine oxides can be easily
obtained in high yields from the reaction of
the cheap and easily-handled diethyl
phosphite with Grignard reagents via
substituition reactions,16 this method should
facilitate the introduction of a relatively
broad scope of the diarylphosphinyl
functionality into the allenic framework.
Accordingly, we believe that the present
reaction may proceed via similar
a
mechanism as the previously reported Cd-
catalyzed reaction.14 The catalytic cycle is
outlined in Scheme 3. The coordination of
zinc cation to propargyl alcohol 1 may
activate and enable the cleavage of the C-O
bond to generate the propargylic carbon
cation B (resonance structure B’) and C.
Ar2P(O)H 2 is in equilibrium with its
tautomer 2’, and may react with B and C to
produce the propargylic phosphonite
intermediate D via the attack of oxygen
atom to the propargylic position and
generate one molecule of water. The
Table 3 Zn(OTf)2-catalyzed C-P coupling of 1a with
diarylphosphine oxides 2b-2ga
We further performed
a
control
experiment to understand the reaction
mechanism (Scheme 2). An equal molar
mixture of 1a, 1g and 2a was heated to 100
oC for 12 h in the presence of 10 mol% of
Zn(OTf)2. Analysis of the crude mixture by
31P NMR shows that a mixture of 3a and 3g
with a ratio of 1.42/1 was formed. In light of
the steric factor of the two substrate (1a vs
1g), this result indicates that a SN2’-type
mechanism by the direct attack of the
phosphorus nucleophile to the triple bond is
less likely.
intermediate
D
finally undergoes the
classical [2,3]-rearrangement to give the
allenyl product 3.
Scheme 3 The proposed mechanism
Scheme 2 The competition experiment
Received xx yyyy 2018 accepted xx yyyy 2018
CONTACT: Ruwei Shen, State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech
University, Nanjing 210009, China; . Email: shenrw@njtech.edu.cn. †These authors contributed equally.

RUNNING TITLE 50 CHARACTERS OR LESS
reference standard. Chemical shifts are
CONCLUSIONS
In summary, we have found that
expressed in ppm and J values are given in
Hz. HRMS analysis of the products (ESI-
TOF) was performed at the Analytical
Center of State Key Laboratory of
Materials-Oriented Chemical Engineering at
Nanjing Tech University, China. The
Supplemental Materials contains the full
Zn(OTf)2 is a competent catalyst to promote
the dehydrative coupling of propargyl
alcohols with diarylphosphine oxides under
solvent free conditions. The reaction could
generate the allenylphosphine oxides with
high selectivity from several propargyl
alcohols and diarylphosphine oxides in
moderate to high yields. Since the zinc
catalyst is less expensive and more
environmentally friendly, this reaction
should be useful for the preparation of these
products.
1
experimental procedures and copies of H,
31
13C and P NMR spectra of the products 3
(Figures S 2 – S 40).
A typical procedure for the Zn(OTf)2-
catalyzed reaction of propargyl alcohols
with diarylphosphine oxide (Synthesis of 3a):
An oven-dried Schlenk tube containing a
Teflon-coated stir bar was charged with
Zn(OTf)2 (7.3 mg, 0.02 mmol), propagylic
alcohol 1a (75.4 mg, 0.4 mmol,) and
diphenylphosphine oxide 2a (40.4 mg, 0.2
mmol). The Schlenk tube was sealed and
then evacuated and backfilled with N2
(3 cycles). The Schlenk tube was sealed and
immersed in an oil bath which was heated to
EXPERIMENTAL
General information: all reactions were
performed under dry N2 atmosphere.
Anhydrous solvents were distilled prior to
use: THF was distilled from sodium using
benzophenone as the indicator; MeCN,
DCM and DMF were distilled from CaH2.
Flash chromatography was performed on
silica gel using petroleum ether and EtOAc
o
100 C. After the reaction was heated for 12
h, the mixture was disolved in DCM and
transferred into a round-bottom flask.
Removal of the solvent under vacuum left a
slurry residue, which was purified by flash
chromatography on silica (petroleum
ether/ethyl acetate 3/1 to 1/1) to afford 69.2
1
as eluent. H (400 MHz), 13C (100 MHz)
and 31P NMR (162 MHz) spectra were
recorded on a Bruker Ascend(TM) 400 MHz
NMR spectrometer in CDCl3. Chemical
shifts
(ppm)
were
recorded
with
tetramethylsilane (TMS) as the internal

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DOI: 10.1800/10426507.2015
mg of 3a (yield 93%), which is a known
compound.12
ACKNOWLEDGMENT
(4,4-dimethyl-1-phenylpenta-1,2-dien-3-
yl)bis(4-methoxyphenyl)phosphine oxide
(3t): 63.9 mg (yield 82%), prepared from
75.4 mg of 1a (0.4 mmol) and 44.0 mg of 2f
(0.2 mmol) according to the typical
We thank the support from the National
Natural Science Foundation of China
(21302095), Jiangsu Provincial NSFC
(BK20130945)
University.
and
Nanjing
Tech
1
procedure for the synthesis of 3a. H NMR
(CDCl3, 400 MHz): δ = 7.79-7.57 (m, 4H),
7.54-7.31 (m, 2H), 7.26–7.17 (m, 4H), 7.13-
7.08 (m, 1H), 7.03-6.98 (m, 2H), 6.89-6.84
(m, 1H), 6.06-6.01 (m, 1H), 1.34 (s, 4.5H),
1.33 (s, 4.5H). 31P NMR (CDCl3, 162 MHz):
δ = 29.13, 29.08. HRMS (ESI-TOF): m/z =
391.1618, calcd for C25H25FOP [MH+]
391.1627.
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University, Nanjing 210009, China; . Email: shenrw@njtech.edu.cn. †These authors contributed equally.

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University, Nanjing 210009, China; . Email: shenrw@njtech.edu.cn. †These authors contributed equally.

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Alcohols with P(O)H Compounds for the
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10. For our recent contributions on the topic, also
see: (a) Shen, R.; Yang, J.; Zhao, H.; Fu, Y.;
Received xx yyyy 2018 accepted xx yyyy 2018
CONTACT: Ruwei Shen, State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech
University, Nanjing 210009, China; . Email: shenrw@njtech.edu.cn. †These authors contributed equally.

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ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1800/10426507.2015
Conditions. Org. Lett. 2016, 18, 6066-6069. DOI:
10.1021/acs.orglett.6b03028.
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13. Miao, L.-L.; Li, Y.-H.; Yang, S.-D. Silver-
catalyzed Phosphonylation of Unprotected
Propargylic Alcohols for the Synthesis of
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15. Cadmium is known as an extremely toxic
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14. (a) Yang, J.; Zhang, M.; Qiu, K.; Wang, L.; Yu,
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of Propargyl Alcohols with Diarylphosphine
Oxides to Afford Allenylphosphine Oxides. Adv.
16. Busacca, C. A.; Lorenz, J. C.; Grinberg, N.;
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Received xx yyyy 2018 accepted xx yyyy 2018
CONTACT: Ruwei Shen, State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech
University, Nanjing 210009, China; . Email: shenrw@njtech.edu.cn. †These authors contributed equally.

Phosphorus, Sulfur and Silicon, 193: xxxx-yyyy, 2018
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DOI: 10.1800/10426507.2015
Scheme 1. The development of synthetic methods to access allenylphosphoryl compounds
Received xx yyyy 2018 accepted xx yyyy 2018
CONTACT: Ruwei Shen, State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech
University, Nanjing 210009, China; . Email: shenrw@njtech.edu.cn. †These authors contributed equally.

Phosphorus, Sulfur and Silicon, 193: xxxx-yyyy, 2018
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ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1800/10426507.2015
Table 1. Optimization of the reaction conditions of 1a and 2aa
aReaction conditions: 1a (0.24 mmol), 2a (0.2 mmol), [Zn] (10 mol%), solvent (2 mL).
bIsolated yields.
cNS: no solvent.
d1-(diphenylphosphoryl)-4,4-dimethyl-1-phenylpentan-3-one was isolated in 12% yield.
e1a (0.4 mmol) and 2a (0.2 mmol) were used.
f1-(diphenylphosphoryl)-4,4-dimethyl-1-phenylpentan-3-one was isolated in 44% yield.
Received xx yyyy 2018 accepted xx yyyy 2018
CONTACT: Ruwei Shen, State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech
University, Nanjing 210009, China; . Email: shenrw@njtech.edu.cn. †These authors contributed equally.

Phosphorus, Sulfur and Silicon, 193: xxxx-yyyy, 2018
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ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1800/10426507.2015
Table 2. Zn(OTf)2-catalyzed C-P coupling of propargylic alcohols 1 with diarylphosphine oxide 2aa
entry
1
R1
R2
R3
H
3, yield (%)
3a, 93
1
tBu
tBu
tBu
tBu
tBu
tBu
nBu
nBu
nBu
nBu
tBu
nBu
tBu
Ph
Ph
1a
1b
1c
1d
1e
1f
2
4-ClC6H4
4-FC6H4
4-BrC6H4
2-ClC6H4
4-MeOC6H4
Ph
H
3b, 95
3
H
3c, 94
4
H
3d, 95
5
H
3e, 81
6
H
3f, 87b
7
H
3g, 74
1g
1h
1i
8
4-FC6H4
4-CF3C6H4
4-MeOC6H4
Ph
H
3h, 72
9
H
3i, 47
10
11
12
13
14
15
H
3j, 78b
1j
Ph
Ph
3k, 95
1k
1l
Ph
3l, 67
-(CH2)5-
Ph
3m, trace (26)c
3n, 20 (trace)c
3o, 37 (15)c
1m
1n
1o
H
H
C3H5
Ph
a unless otherwise noted, the reaction conditions: 1 (0.4 mmol), 2 (0.2 mmol), Zn(OTf)2 (10 mol%), no solvent, 100
oC; Isolated yields are given.
b Combined yields of the mixture of allenyl diphenylphosphine oxide and propargylic diphenylphosphine oxide
isomer (ratio: ca. 1/5).
c 1 (0.4 mmol), 2 (0.2 mmol), ZnCl2 (10 mol%), MeCN (2 mL), 100 oC.
Received xx yyyy 2018 accepted xx yyyy 2018
CONTACT: Ruwei Shen, State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech
University, Nanjing 210009, China; . Email: shenrw@njtech.edu.cn. †These authors contributed equally.

Phosphorus, Sulfur and Silicon, 193: xxxx-yyyy, 2018
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ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1800/10426507.2015
Table 3. Zn(OTf)2-catalyzed C-P coupling of 1a with diarylphosphine oxides 2b-2ga
a Reaction conditions: 1a (0.4 mmol), 2 (0.2 mmol), Zn(OTf)2 (10 mol%), no solvent, 100 oC; Isolated yields are
given.b The dr value was determined from 31P NMR spectra of the product.
Received xx yyyy 2018 accepted xx yyyy 2018
CONTACT: Ruwei Shen, State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech
University, Nanjing 210009, China; . Email: shenrw@njtech.edu.cn. †These authors contributed equally.

Phosphorus, Sulfur and Silicon, 193: xxxx-yyyy, 2018
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ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1800/10426507.2015
Scheme 2. The competition experiment
Scheme 3. The proposed mechanism
Received xx yyyy 2018 accepted xx yyyy 2018
CONTACT: Ruwei Shen, State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech
University, Nanjing 210009, China; . Email: shenrw@njtech.edu.cn. †These authors contributed equally.

Phosphorus, Sulfur and Silicon, 193: xxxx-yyyy, 2018
Copyright © Taylor and Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1800/10426507.2015
Received xx yyyy 2018 accepted xx yyyy 2018
CONTACT: Ruwei Shen, State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech
University, Nanjing 210009, China; . Email: shenrw@njtech.edu.cn. †These authors contributed equally.