Copper-Catalyzed Allenylation-Isomerization Sequence of Penta-1,4-diyn-3-yl Acetates with P(O)H Compounds: Facile Synthesis of 1-Phosphonyl 2,4-Diynes

Article abstract of DOI:10.1002/adsc.201600684

The copper-catalyzed reaction of 5-substituted penta-1,4-diyn-3-yl acetates with P(O)H compounds to efficiently give a new class of phosphonyl diynes is reported. The reaction may take place through a regioselective nucleophilic attack of phosphorus nucleophiles on Cu-allenylidene intermediates to form allenyl intermediates followed by a rapid allene-alkyne isomerization process. The synthetic utility of the obtained products is demonstrated. (Figure presented.).

Full text of DOI:10.1002/adsc.201600684

UPDATES
DOI: 10.1002/adsc.201600684
Copper-Catalyzed Allenylation-Isomerization Sequence of Penta-
,4-diyn-3-yl Acetates with P(O)H Compounds: Facile Synthesis
of 1-Phosphonyl 2,4-Diynes
1
a,
a
a
a
b,
Ruwei Shen, * Jianlin Yang, Bing Luo, Lixiong Zhang, and Li-Biao Han *
a
State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry and Chemical Engineering,
Nanjing Tech University, Nanjing 210009, Peopleꢀs Republic of China
E-mail: shenrw@njtech.edu.cn
National Institute of Advanced Industrial Science & Technology (AIST), Tsukuba, Ibaraki 305–8565, Japan
b
E-mail: libiao-han@aist.go.jp
Received: June 29, 2016; Revised: August 26, 2016; Published online: && &&, 0000
Supporting information for this article can be found under: http://dx.doi.org/10.1002/adsc.201600684.
Abstract: The copper-catalyzed reaction of 5-substi-
tuted penta-1,4-diyn-3-yl acetates with P(O)H com-
pounds to efficiently give a new class of phosphonyl
diynes is reported. The reaction may take place
through a regioselective nucleophilic attack of phos-
phorus nucleophiles on Cu-allenylidene intermedi-
ates to form allenyl intermediates followed by
a rapid allene-alkyne isomerization process. The
synthetic utility of the obtained products is demon-
strated.
almost arbitrary regio- and stereoselectivity by choos-
[3]
ing suitable catalysts and conditions (Figure 1a).
The C ÀP couplings of P(O)H compounds with ter-
sp
minal or functionalized alkynes were extensively ex-
plored in recent years, and some extremely useful
methods have been established for alkynylphosphorus
[
4]
compounds (Figure 1b).
In comparison, the straightforward methods for the
synthesis of phosphonyl 1,3-dienes and 1,2-dienes (al-
lenes) via catalytic transformations of P(O)ÀH bonds
remain underdeveloped (Figure 1c and d). Particular-
ly, there is only one report in the literature describing
the access of phosphonyl 1,3-dienes from a Ni-cata-
lyzed reaction of propargyl alcohols with P(O)H com-
pounds, whereby the regioselectivity is not satisfacto-
Keywords: allenes; copper catalysis; CÀP bond for-
mation; diynes; organophosphorus compounds
[
5]
ry. The high demand for these compounds in cycliza-
tions and related reactions for constructing structural-
Introduction
The importance of organophosphorus compounds in
organic synthesis, biology and material science has
stimulated extensive studies on developing new and
efficient CÀP bond-forming reactions for introducing
[
1]
a phosphorus functionality into organic molecules.
To this end, the catalytic reactions of P(O)H com-
pounds such as H-phosphonates, H-phosphinates and
secondary phosphine oxides with functional groups of
unsaturated C-C or C-heteroatom bonds represent
[2]
a powerful tool. Particularly, the transition metal
TM)-catalyzed reactions of P(O)H compounds with
(
alkynes are extremely useful as this methodology
could enable the formation of a wide range of valua-
ble
unsaturated
phosphorus
compounds
[3–5,8]
(
Figure 1).
For example, the TM-catalyzed addi-
tions of P(O)H compounds to the CꢀC triple bonds,
which have been studied for more than 20 years, Figure 1. Transition metal-catalyzed reactions of alkynes
could provide vinylphosphorus compounds with with P(O)H compounds: a brief background.
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ly more sophisticated organophosphorus compounds Table 1. Effect of the Cu-catalytic systems on reaction of 1a
[a]
and 2a.
consequently stimulates the development of alterna-
[6,7]
tive methods.
A few synthetic methods for phos-
phonyl 1,3-dienes have been recently reported based
[
6a–c]
on the transformations of phosphonyl allenes.
As an interest in developing new CÀP bond-form-
ing reactions for efficient organophosphorus synthe-
[
8]
sis, we recently reported a highly selective Cu-cata-
lyzed propargylic substitution of propargyl acetates
with P(O)H compounds to address the synthesis of al-
[
8a,9]
lenylphosphorus compounds (Figure 1d).
The new
reaction is believed to proceed via a unique nucleo-
philic interception of in situ generated Cu-allenyli-
dene intermediates by phosphorus nucleophiles.
While most of the propargyl acetates studied were
found to be selectively transformed to the corre-
sponding allenyl derivatives in high yields under mild
and green conditions, during the course of our further
study on the reaction we came across a different out-
come from the reaction of 5-substituted penta-1,4-
diyn-3-yl acetates, which gave 1-phosphonyl 2,4-
diynes as the products (Figure 1e). We reason that an
interesting facile catalytic allenylation–isomerization
sequence may happen in the reaction thus ultimately
leading to the formation of these new products. Rec-
ognizing the versatile reactivity of the conjugated
[a]
Reaction conditions: 1a (0.24 mmol), 2a (0.2 mmol), [Cu]
5 mol%), ligand (6 mol%) and (i-Pr) NEt (0.22 mmol),
EtOH (2 mL).
Isolated yields.
(
2
[b]
[10]
[1a,b]
diyne unit and the phosphorus functionality,
we regard to the ligand, 2,2’-bpy and 1,10-Phen were
consider that these diyne derivatives would be useful found to be active to catalyze the reaction with CuI
[10]
building blocks to access valuable compounds with and gave the product in comparable yields in 4 h.
advanced molecular structures upon further synthetic Nevertheless, only a trace amount of 3a was detected
manipulation. As a result, we report herein the results when a bisphosphine ligand DPPE was used. In addi-
of this study, namely, the preparation and synthetic tion, no reaction took place in the absence of
application of a new class of 1-phosphonyl 2,4-diyne a copper catalyst. Compound 3a was characterized by
1
13
31
derivatives from an efficient Cu-catalyzed allenylation
H, C, P NMR and HR-MS, and the proposed
and allene–alkyne isomerization reaction of 5-substi- linear conjugated diyne structure was unambiguously
tuted penta-1,4-diyn-3-yl acetates with P(O)H com- confirmed by the X-ray diffraction analysis of a single
[
11]
pounds (Figure 1e). To the best of our knowledge, crystal of the product (Figure 2).
such a highly efficient transformation based on
P(O)H compounds and alkynes has not been dis-
Table 2 summarizes the results of some typical di-
AHCTUNGTREGyNNUN nylphosphorus compounds, prepared from 5-substi-
closed and there is no report on the synthesis of phos- tuted penta-1,4-diyn-3-yl acetates with P(O)H com-
phoryl 1,3-diynyl compounds.
pounds, by taking advantage of the present Cu-cata-
lyzed method. Thus, in addition to 2a, other diaryl-
Results and Discussion
As shown in Table 1, when 5-phenylpenta-1,4-diyn-3-
yl acetate (1a) and diphenylphosphine oxide (2a)
were treated with a catalytic amount of CuI and
TMEDA in the presence of 1.1 equiv. of (i-Pr) NEt in
2
EtOH at 08C for 2 h, the reaction gave the phosphon-
yl diyne 3a in 81% yield highly selectively (entry 1).
The reaction could also be promoted by the combina-
tion of other copper salts and and ligands. For exam-
ple, the use of CuBr and CuCl with TMEDA gave 3a
in 81% and 80% yield, respectively. Divalent Cu salts
Cu(OAc) and CuCl are also active to promote the Figure 2. Molecular structure of compound 3a (ellipsoids are
2
2
reaction, albeit giving 3a in slightly low yields. With drawn at 30% probability).
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[a]
Table 2. Scope of the reaction.
[
[
a]
b]
Reaction conditions: 1 (0.24 mmol), 2 (0.2 mmol), CuI (5 mol%), TMEDA (6 mol%) and (i-Pr) NEt (0.22 mmol), EtOH
2
(2 mL). Isolated yields are given.
10 mmol scale.
ACHTUNGTRENNUNGp hosphine oxides (2b–2e) bearing either electron-do- yield. Notably, the reaction is also easily scaled up to
nating or electron-withdrawing substitutes on the a gram-scale, to give 1.85 g of the desired product 3f
phenyl rings are applicable to produce the desired in 75% isolated yield. The reaction of H-phosphinate
products in good yields. Particularly, the reaction of 2i enables the successful synthesis of the phosphorus-
the more sterically hindered substrate 2e which bears tethered 1,7,9-ene-diyne products 3i and 3p in 71%
two o-tolyl substituents also took place smoothly to and 74% yields, respectively. With regard to 1, the
give the product 3e in 75% yields. Furthermore, H- substrates with the electron-donating (1b, R=p-
phosphonates and H-phosphinates also readily react- MeC H ) and electron-withdrawing phenyl substitu-
6
4
ed with 1a to give the desired products in good to ents (1c, R=p-FC H ) at the 5-position were exam-
6
4
high yields (3f–3i). For example, the reaction of di- ined, which gave the products 3j–3m in good to high
methyl phosphonate (2f) with 1a gave dimethyl (5- yields. Furthermore, the alkyl substituted substrate 1d
phenylpenta-2,4-diyn-1-yl) phosphonate (3g) in 80% (R=n-C H ) was also applicable, producing the de-
6
13
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Scheme 1. A plausible mechanism.
sired products 3n–3p in good yields without any loss
of efficiency.
occurrence of the ene-diyne unit in bioactive mole-
A plausible mechanism for the reaction is proposed cules and functional materials, such a transformation
[
12]
[14]
in Scheme 1, based on literature precedents
and would find utility in related areas.
[
8a]
a report of our previous work. In the presence of
On the other hand, the conjugated diynes are val-
[10]
a base, the active Cu(I) species A generated from the uable building blocks for heterocyclic synthesis. Ac-
reaction of the copper salt with TMEDA first reacts cordingly, the synthetic value of the obtained products
with 1 to produce the Cu-acetylide complex B. Loss is further highlighted as promising precursors to
of an acetyl group from B would form a copper alle- access heterocycle-containing organophosphorus com-
[
12d]
nylidene complex C.
The reaction of 2 with C via pounds. As shown in Scheme 2b, the cyclization of 3a
a regioselective nucleophilic attack then produces the with hydroxylamine afforded the isoxazole-tethered
yne-allenyl Cu-intermediate D, protodemetallation of phosphine oxides 6a and 6b in 68% yield with a selec-
[
15]
which gives the yne-allenyl intermediate E and regen- tivity of 83/17. Upon treatment of the 1-phosphonyl
erate the copper catalyst. The unstable E finally un- 2,4-diyne products with hydrazine, pyrazole-tethered
dergoes an allene–alkyne isomerization to give the phosphine oxides 7a–7d were successfully obtained in
product 3.
good
yields
with
excellent
regioselectivity
It is impossible to trap the intermediate E by short- (Scheme 2c). Products 6 and 7 are characterized by
1
13
31
ening the reaction time due to the rapid rate of the
H, C, P NMR and HR-MS, and the structures are
isomerization process. Nevertheless, the reaction of further confirmed by the single crystal X-ray diffrac-
-methyl-5-(p-tolyl)penta-1,4-diyn-3-yl acetate (1e) tion analyses of the representative compounds 6a and
[
13]
3
[
16]
with 2a produced yne-allenyl product 4 in 85% yield 7a (Figure 3). It is worth noting that further reduc-
[
Eq. (1)], confirming the proposed route involving the tion of the P=O functionality of these products should
[
8a]
formation of intermediate E. In addition, the par- enable an access to N,P-bidentate ligands.
ticipation of the solvent proton during the isomeriza-
tion process is evident as the reaction of 1a and 2g
performed in CH OD gave the deuterated product Conclusions
3
3
g-d (a-D ca. 94%) in 83% yield [Eq. (2)].
It should be noted that the resulting 1-phosphonyl In conclusion, we have disclosed a highly efficient
,4-diynes are highly useful in organic synthesis due copper-catalyzed reaction of 5-substituted penta-1,4-
2
to the vesertile reactivity of the conjugated diyne unit diyn-3-yl acetates with P(O)H compounds to afford
and the phosphorus functionality. For example, the a facile synthesis of a new class of phosphonyl 1,3-
products could serve as valuable precusors for intro- diynes. The reaction takes place efficiently under mild
ducing an ene-diyne unit into an organic molecule via conditions, and the products are useful to access ad-
Horner–Wadsworth–Emmons (HWE) type reactions. vanced molecular structures with further elaboration.
As shown in Scheme 2a, treatment of 3f with We believe that this reaction will attract attention
1
.1 equiv. of LiHMDS at À788C followed by the addi- from many research disciplines due to the broad utili-
tion of 1-pyrenecarbaldehyde successfully gave the ty of the 1,3-diynes and the organophosphorus com-
olefinic product 5 in 65% yield. In light of the wide pounds.
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Scheme 2. Synthetic transformation of the products.
Figure 3. Molecular structures of compounds 6a and 7a (ellipsoids are drawn at 30% probability).
1
13
using petroleum ether and EtOAc as eluent. H, C and
3
1
Experimental Section
P NMR spectra were recorded on a Bruker Advance 400
spectrometer. Chemical shifts were recorded with tetrame-
thylsilane (TMS) as the internal reference standard. Chemi-
cal shifts are expressed in ppm and J values are given in Hz.
HR-MS were obtained from the Analytical Center of the
Department of Chemistry of Zhejiang University, P.R.
China.
General Information
Unless otherwise specified, all reactions were performed
under a dry N atmosphere. The substrates 2a, 2f and 2g are
2
commercially available and were used as received. Other
P(O)H compounds were all known and prepared following
[17]
known methods.
Copper salts, TMEDA, 2,2’-bpy, 1,10-
Synthetic Procedure for the Propargyl Acetate 1a
Phen, dppe and (i-Pr) NEt are all commercially available
2
and used as received. Absolute alcohol was used after de-
gassing. Flash chromatography was performed on silica gel
n-Butyllithium (4 mL, 2.5M in hexane) was added to a solu-
tion of ethynylbenzene (1.122 g, 11 mmol) in THF (30 mL)
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at À788C under an N atmophere. The reaction mixture was General Procedure for the Cu-Catalyzed Preparation
2
allowed to stir at this temperature for 30 min. 3-(Trimethyl-
silyl)propiolaldehyde (1.262 g, 10 mmol) was then slowly
of Phosphoryl 1,3-Diynes
An oven-dried Schlenk tube containing a Teflon-coated stir
bar was charged with CuI (1.9 mg, 5 mol%). The Schlenk
added and the reaction mixture was stirred at À788C for
30 min, naturally warmed to room temperature and kept
tube was sealed and then evacuated and backfilled with N2
stirring overnight. After being quenched by saturated
NH Cl solution, extracted with Et O and concentrated to
(
3 cycles). 1.0 mL of ethanol was injected, followed by the
4
2
injection of TMEDA (2 mL) and (i-Pr) NEt (38 mL) under
stirring. The mixture was stirred for 10 min and cooled to
dryness, the residue was dissolved in THF and cooled to
2
0
8C.
A solution of tetrabutylammonium fluoride (ca.
0
8C. Then 1 (0.24 mmol) and 2 (0.2 mmol) dissolved in
10 mmol, 85% purity containing water) in THF was added
dropwise. After stirred at 08C for 2 h, the reaction mixture
was quenched with water and extracted with ether. The or-
1.0 mL of ethanol were injected. The reaction was kept stir-
ring at the same temperature and monitored by TLC. After
the reaction was complete, removal of the solvent under
vacuum left a slurry residue, which was purified by flash
chromatography on silica (PE/EtOAc 3:1 to 1:1 v/v) to
afford the product 3.
ganic layers were dried with MgSO , and concentrated
4
under vacuum. Pure 1-phenylpenta-1,4-diyn-3-ol was ob-
tained after column chromategraphy on silica gel (PE/
EtOAc 8:1 v/v); yield: 1.250 g (80%).
To a solution containing the above prepared alcohol
Diphenyl(5-phenylpenta-2,4-diyn-1-yl)phosphine
oxide
(
5 mmol, 780.0 mg), acetic acid (6 mmol, 360.0 mg) and N,
(3a): Yield: 55.1 mg (81%); white solid; mp 152–1538C;
1
N-dimethylpyridin-4-amine (DMAP, 0.5 mmol, 61.0 mg) in
H NMR (CDCl , 400 MHz): d=7.87–7.81 (m, 4H), 7.60–
3
CH Cl (10 mL) was added a solution of dicyclohexylmeth-
7.49 (m, 6H), 7.44–7.42 (m, 2H), 7.33–7.26 (m, 3H), 3.44 (d,
2
2
1
3
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
anediimine (DCC, 6 mmol, 1.236 g) in CH Cl at 08C. After
J=16.8 Hz, 2H); C NMR (CDCl , 100 MHz): d=132.5,
2
2
3
the addition was complete, the reaction was stirred at 08C
for 2 h. The reaction mixture was filtered and concentrated.
The residue was purified by column chromatography on
silica gel (PE/EtOAc 20:1 v/v) to afford 1-phenylpenta-1,4-
132.4 (d, JP,C =2.1 Hz), 131.1 (d, JP,C =102.3 Hz), 131.2 (d,
JP,C =9.4 Hz), 129.1, 128.6 (d, JP,C =12.3 Hz), 128.3, 121.3 (d,
JP,C =1.3 Hz), 76.3 (d, JP,C =3.6 Hz), 74.2 (d, JP,C =11.6 Hz),
73.7 (d, J =5.5 Hz), 69.4 (d, JP,C =9.2 Hz), 23.8 (d, JP,C
=
P,C
3
1
diyn-3-yl acetate 1a as a liquid; yield: 851.4 mg (86%).
67.2 Hz); P NMR (CDCl , 162 MHz): d=28.1; HR-MS
3
1
+
H NMR (CDCl , 400 MHz): d=7.50–7.47 (m, 2H), 7.36–
(EI-TOF): m/z=340.1022, calcd. for C H OP [M ]:
3
23 17
7
1
1
.31 (m, 3H), 6.28 (d, J=2.4 Hz, 1H), 2.62 (d, J=2.4 Hz,
340.1017.
1
3
H), 2.17 (s, 3H); C NMR (CDCl , 100 MHz): d=169.1,
3
(5-Phenylpenta-2,4-diyn-1-yl)di-p-tolylphosphine
oxide
32.1, 129.2, 128.3, 121.4, 85.4, 82.1, 77.5, 73.7, 53.3, 20.8;
(
3b): Yield: 56.0 mg (76%); white solid; mp 147–1488C;
+
1
HR-MS (EI-TOF): m/z=198.0683, calcd. for C H O [M ]:
1
3
10
2
H NMR (CDCl , 400 MHz): d=7.70–7.65 (m, 4H), 7.42–
3
198.0681.
7
2
.39 (m, 2H), 7.33–7.24 (m, 7H), 3.36 (d, J=17.2 Hz, 2H),
Compounds 1b–1d were prepared following a similar pro-
cedure described as above. 1a–1d are stable at least for 8
months at 08C stored in a refrigerator.
13
.39 (s, 6H); C NMR (CDCl , 100 MHz): d=143.0 (d,
3
JP,C =2.5 Hz), 132.4, 132.3 (d, JP,C =9.5 Hz), 129.3 (d, JP,C
2.0 Hz), 129.1, 128.2, 127.3 (d, JP,C =104.9 Hz), 121.3 (d,
JP,C =1.4 Hz), 76.2 (d, JP,C =3.4 Hz), 74.5 (d, JP,C =11.3 Hz),
=
1
1
-(p-Tolyl)penta-1,4-diyn-3-yl
acetate
(1b):
Yield:
1
9
7
2
3
1
22.1 mg (87%); liquid; H NMR (CDCl , 400 MHz): d=
.37 (d, J=8.4 Hz, 2H), 7.13 (d, J=8.4 Hz, 2H), 6.27 (d, J=
.4 Hz, 1H), 2.61 (d, J=2.0 Hz, 1H), 2.35 (s, 3H), 2.16 (s,
H); C NMR (CDCl , 100 MHz): d=169.1, 139.4, 131.9,
29.0, 118.3, 85.6, 81.5, 77.7, 73.5, 53.4, 21.5, 20.8; HR-MS
3
73.8 (d, JP,C =6.7 Hz), 69.1 (d, J =8.5 Hz), 23.5 (d, JP,C
=
P,C
31
6
7.8 Hz), 21.6; P NMR (CDCl , 162 MHz): d=29.8; HR-
3
+
MS (EI-TOF): m/z=368.1336, calcd. for C H OP [M ]:
2
5
21
13
3
3
68.1330.
Bis(4-methoxyphenyl)(5-phenylpenta-2,4-diyn-1-yl) phos-
phine oxide (3c): Yield: 64.1 mg (80%); white solid; mp
+
(
EI-TOF): m/z=212.0837, calcd. for C H O [M ]:
1
4
12
2
212.0837.
1
1
4
4
60–1618C; H NMR (CDCl , 400 MHz): d=7.78–7.73 (m,
3
1
-(4-Fluorophenyl)penta-1,4-diyn-3-yl acetate (1c): Yield:
H), 7.46–7.44 (m, 2H), 7.37–7.28 (m, 3H), 7.03–7.00 (m,
1
8
7
1
74.8 mg (81%); liquid; H NMR (CDCl , 400 MHz): d=
.48–7.45 (m, 2H), 7.04–6.99 (m, 2H), 6.25 (d, J=2.4 Hz,
H), 2.61 (d, J=2.0 Hz, 1H), 2.16 (s, 3H); C NMR
13
3
H), 3.87 (s, 6H), 3.38 (d, J=16.8 Hz, 2H); C NMR
(
CDCl , 100 MHz): d=162.7 (d, J =2.3 Hz), 133.2 (d,
1
3
3
P
,
C
JP,C =11.0 Hz), 132.5, 129.1, 128.3, 122.3 (d, JP,C =109.3 Hz),
21.4, 114.2 (d, JP,C =13.2 Hz), 76.2 (d, JP,C =2.6 Hz), 74.8 (d,
(
CDCl , 100 MHz): d=169.0, 163.0 (d, J=249.3 Hz), 134.1
3
1
(
d, J=8.4 Hz), 117.4 (d, J=3.4 Hz), 115.6 (d, J=22.2 Hz),
JP,C =10.7 Hz), 73.8 (d, JP,C =6.8 Hz), 69.1 (d, J =9.3 Hz),
P,C
8
2
4.3, 82.0, 77.4, 73.7, 53.2, 20.7; HR-MS (EI-TOF): m/z=
31
5
5.3, 24.1 (d, JP,C =67.9 Hz); P NMR (CDCl , 162 MHz):
+
3
16.0588, calcd for C H O F [M ]: 216.0587.
1
3
9
2
d=28.7; HR-MS (EI-TOF): m/z=400.1222, calcd. for
Undeca-1,4-diyn-3-yl acetate (1d): Yield: 855.0 mg (83%);
+
1
C
25
H
21
O
3
P [M ]: 400.1228.
Bis(4-fluorophenyl)(5-phenylpenta-2,4-diyn-1-yl)
phine oxide (3d): Yield: 58.6 mg (78%); white solid; mp
liquid; H NMR (CDCl , 400 MHz): d=6.01 (dd, J =4.0 Hz,
3
1
phos-
J =2.0 Hz, 1H), 2.53 (d, J=2.0 Hz, 1H), 2.22 (td, J =
2
1
7
0
1
1
.6 Hz, J =2.0 Hz, 2H), 2.12 (s, 3H), 1.55–1.27 (m, 8H),
2
1
1
3
146–1478C; H NMR (CDCl
, 400 MHz): d=7.88–7.82 (m,
3
.88 (t, J=6.8 Hz, 3H); C NMR (CDCl , 100 MHz): d=
3
4
1
H), 7.46–7.44 (m, 2H), 7.36–7.21 (m, 7H), 3.44 (d, J=
69.2, 87.1, 78.2, 73.6, 73.0, 53.3, 31.3, 28.5, 28.1, 22.5, 20.8,
1
3
7.2 Hz, 2H); C NMR (CDCl , 100 MHz): d=165.4 (dd,
3
8.7, 14.0; HRMS (EI-TOF): m/z=206.1304, calcd. for
+
J
8
3
F,C =252.7 Hz, JP,C =2.9 Hz), 133.8 (dd, JF,C =11.2 Hz, JP,C
.9 Hz), 132.6, 129.3, 128.4, 126.9 (dd, JP,C =105.9 Hz, JF,C
.6 Hz), 121.1, 116.2 (dd, JF,C =21.2 Hz, JP,C =13.2 Hz), 76.7
=
=
C H O [M ]: 206.1307.
13
18
2
(
d, JP,C =3.9 Hz), 73.7 (d, JP,C =11.7 Hz), 73.4 (d, JP,C
=
7
.1 Hz), 69.8 (d, JP,C =8.3 Hz), 24.1 (d, JP,C =68.4 Hz);
Adv. Synth. Catal. 0000, 000, 0 – 0
6
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

UPDATES
asc.wiley-vch.de
3
1
P NMR (CDCl , 162 MHz): d=26.9 (br); HR-MS (EI-
162 MHz): d=35.7; HR-MS (EI-TOF): m/z=320.0964,
3
+
+
TOF): m/z=376.0834, calcd. for C H OPF [M ]: 376.0829.
calcd. for C H O P [M ]: 320.0966.
2
3
15
2
20 17
2
(
5-Phenylpenta-2,4-diyn-1-yl)di-o-tolylphosphine
oxide
Di-p-tolyl(5-(p-tolyl)penta-2,4-diyn-1-yl)phosphine oxide
(
3e): Yield: 55.2 mg (75%); white solid; mp 138–1398C;
(3j): Yield: 61.0 mg (80%); white solid; mp 144–1458C;
1
1
H NMR (CDCl , 400 MHz): d=7.69–7.63 (m, 2H), 7.49–
H NMR (CDCl , 400 MHz): d=7.74–7.69 (m, 4H), 7.34–
3
3
7
.41 (m, 4H), 7.33–7.26 (m, 7H), 3.55 (d, J=16.0 Hz, 2H),
7.29 (m, 6H), 7.09 (d, J=8.0 Hz, 2H), 3.39 (d, J=16.8 Hz,
13
13
2.46 (s, 6H); C NMR (CDCl , 100 MHz): d=142.3 (d,
2H), 2.41 (s, 6H), 2.33 (s, 3H);
C NMR (CDCl3,
3
JP,C =8.3 Hz), 132.5, 132.4 (d, JP,C =2.4 Hz), 132.1 (d, JP,C
=
100 MHz): d=142.8 (d, JP,C =3.2 Hz), 139.5, 132.4, 131.3 (d,
JP,C =10.4 Hz), 129.3 (d, JP,C =12.6 Hz), 129.1, 128.0 (d, JP,C
104.6 Hz), 118.3 (d, JP,C =1.4 Hz), 76.5 (d, JP,C =3.7 Hz), 74.2
(d, JP,C =11.1 Hz), 73.3 (d, JP,C =6.5 Hz), 69.3 (d, J
1
1
7
5
0.9 Hz), 131.8 (d, JP,C =11.2 Hz), 129.6 (d, JP,C =100.2 Hz),
29.1, 128.3, 125.7 (d, JP,C =12.1 Hz), 121.5 (d, JP,C =1.2 Hz),
6.4 (d, JP,C =3.2 Hz), 74.2 (d, JP,C =12.2 Hz), 73.8 (d, JP,C
.6 Hz), 69.7 (d, J =8.7 Hz), 23.5 (d, JP,C =67.4 Hz), 21.3
=
=
=
P,C
3
1
8.9 Hz), 24.0 (d, JP,C =67.3 Hz), 21.6, 21.5; P NMR (CDCl3,
P,C
3
1
(
d, JP,C =3.8 Hz); P NMR (CDCl , 162 MHz): d=34.2;
162 MHz): d=28.5; HR-MS (EI-TOF): m/z=382.1494,
3
+
HR-MS (EI-TOF): m/z=368.1331, calcd. for C H OP
calcd. for C H OP [M ]: 382.1487.
2
5
21
26 23
+
[
M ]: 368.1330.
[5-(4-Fluorophenyl)penta-2,4-diyn-1-yl]di-p-tolyl
phos-
Dimethyl (5-phenylpenta-2,4-diyn-1-yl)phosphonate (3f):
phine oxide (3k): Yield: 61.0 mg (79%); white solid; mp
1
1
Yield: 39.7 mg (80%); yellow liquid; H NMR (CDCl3,
00 MHz): d=7.42–7.40 (m, 2H), 7.31–7.21 (m, 3H), 3.80
149–1508C; H NMR (CDCl , 400 MHz): d=7.73–7.68 (m,
3
4
(
4H), 7.43–7.40 (m, 2H), 7.33–7.30 (m, 4H), 7.00–6.96 (m,
1
3
13
d, J=10.4 Hz, 6H), 2.90 (d, J=22.4 Hz, 2H); C NMR
2H), 3.39 (d, J=16.4 Hz, 2H), 2.41 (s, 6H); C NMR
(
CDCl , 100 MHz): d=132.5 (d, J =1.3 Hz), 129.2, 128.3,
(CDCl , 100 MHz): d=162.8 (d, J =250.3 Hz), 142.9 (d,
3
P,C
3
F,C
1
21.3 (d, JP,C =1.4 Hz), 76.0 (d, JP,C =3.8 Hz), 73.7 (d, JP,C
=
JP,C =3.2 Hz), 134.5 (d, JF,C =7.3 Hz), 131.2 (d, JP,C =9.9 Hz),
129.3 (d, JP,C =12.2 Hz), 127.9 (d, JP,C =105.3 Hz), 117.5 (d,
JF,C =1.1 Hz), 115.7 (d, JF,C =22.4 Hz), 75.0 (d, JP,C =2.7 Hz),
7.6 Hz), 72.9 (d, JP,C =15.8 Hz), 67.6 (d, J =10.4 Hz), 53.6
P,C
3
1
(
1
d, JP,C =6.8 Hz), 18.0 (d, JP,C =144.2 Hz); P NMR (CDCl3,
62 MHz): d=22.6; HR-MS (EI-TOF): m/z=248.0604,
74.6 (d, JP,C =11.9 Hz), 73.6 (d, JP,C =6.5 Hz), 68.9 (d, J
=
P,C
+
31
calcd. for C H O P [M ]: 248.0602.
8.5 Hz), 23.9 (d, JP,C =66.5 Hz), 21.5; P NMR (CDCl3,
162 MHz): d=28.5; HR-MS (EI-TOF): m/z=386.1242,
13
13
3
Diethyl (5-phenylpenta-2,4-diyn-1-yl)phosphonate (3g):
1
+
Yield: 46.4 mg (84%); yellow liquid; H NMR (CDCl3,
calcd. for C H OPF [M ]: 386.1236.
25
20
4
4
6
1
3
00 MHz): d=7.42–7.40 (m, 2H), 7.30–7.21 (m, 3H), 4.19–
[5-(4-Fluorophenyl)penta-2,4-diyn-1-yl]diphenyl
phos-
.11 (m, 4H), 2.87 (d, J=22.4 Hz, 2H), 1.31 (d, J=7.2 Hz,
phine oxide (3l): Yield: 51.6 mg (72%); white solid; mp
1
3
1
H); C NMR (CDCl , 100 MHz): d=132.5 (d, J
=
=
155–1568C; H NMR (CDCl , 400 MHz): d=7.86–7.81 (m,
3
P,C
3
.4 Hz), 129.1, 128.3, 121.4 (d, JP,C =1.5 Hz), 75.8 (d, JP,C
4H), 7.60–7.50 (m, 6H), 7.45–7.41 (m, 2H), 7.01–6.97 (m,
1
3
.2 Hz), 73.8 (d, JP,C =7.2 Hz), 73.4 (d, JP,C =14.7 Hz), 67.4
d, JP,C =10.7 Hz), 63.1 (d, JP,C =6.4 Hz), 19.0 (d, J
2H), 3.44 (d, J=16.4 Hz, 2H); C NMR (CDCl , 100 MHz):
3
(
1
=
d=163.0 (d, JF,C =250.1 Hz), 134.6 (d, JF,C =8.7 Hz), 132.5
P,C
3
1
43.3 Hz), 16.4 (d, JP,C =5.9 Hz);
P NMR (CDCl3,
(d, JP,C =2.0 Hz), 131.3 (d, JP,C =9.6 Hz), 131.2 (d, JP,C
102.7 Hz), 128.7 (d, JP,C =12.0 Hz), 117.5 (d, JF,C =3.7 Hz),
115.8 (d, JF,C =22.3 Hz), 75.3 (d, JP,C =3.7 Hz), 74.3 (d, JP,C
=
162 MHz): d=20.0; HR-MS (EI-TOF): m/z=276.0917,
+
calcd. for C H O P [M ]: 276.0915.
=
15
17
3
Methyl phenyl(5-phenylpenta-2,4-diyn-1-yl) phosphinate
3h): Yield: 41.1 mg (70%); yellow slurry solid; H NMR
11.2 Hz), 73.6 (d, J =8.1 Hz), 69.2 (d, JP,C =8.1 Hz), 23.9
P,C
31
1
(
(d, JP,C =67.2 Hz); P NMR (CDCl , 162 MHz): d=28.0;
3
(
1
3
CDCl , 400 MHz): d=7.93–7.87 (m, 2H), 7.63–7.61 (m,
HR-MS (ESI-TOF): m/z=359.1018, calcd. for C H OPF
[MH ]: 359.1001.
3
23 17
+
H), 7.57–7.52 (m, 2H), 7.49–7.46 (m, 2H), 7.36–7.29 (m,
1
3
H), 3.80 (d, J=11.2 Hz, 3H), 3.22–3.02 (m, 2H); C NMR
Dimethyl [5-(4-fluorophenyl)penta-2,4-diyn-1-yl]phospho-
1
(
(
(
3
(
CDCl , 100 MHz): d=133.1 (d, J =2.4 Hz), 132.5 132.0
nate (3m): Yield: 47.9 mg (90%); yellow liquid; H NMR
3
P,C
d, JP,C =9.4 Hz), 129.1, 128.7 (d, JP,C =13.2 Hz), 128.3, 128.2
d, JP,C =130.2 Hz), 121.4 (d, JP,C =1.5 Hz), 76.0 (d, JP,C
.7 Hz), 73.7 (d, JP,C =7.6 Hz), 73.6 (d, JP,C =12.9 Hz), 68.1
d, JP,C =8.7 Hz), 52.1 (d, J =6.5 Hz), 22.7 (d, JP,C
(CDCl , 400 MHz): d=7.47–7.43 (m, 2H), 7.02–6.97 (m,
3
=
2H), 3.85 (d, J=11.2 Hz, 6H), 2.95 (d, J=22.8 Hz, 2H);
1
3
C NMR (CDCl , 100 MHz): d=163.0 (d, J =250.1 Hz),
3
F
,
C
=
134.6 (dd, JF,C =8.8 Hz, JP,C =1.4 Hz), 117.6 (dd, JF,C =3.4 Hz,
JP,C =1.4 Hz),115.8 (d, JF,C =22.5 Hz), 75.0 (d, JP,C =3.6 Hz),
73.5 (d, JP,C =7.2 Hz, JF,C =1.5 Hz), 73.0 (d, JP,C =16.2 Hz),
P,C
31
9
(
8.0 Hz); P NMR (CDCl , 162 MHz): d=36.8; HR-MS
3
+
EI-TOF): m/z=294.0812, calcd. for C H O P [M ]:
18 15 2
2
94.0810.
67.5 (d, JP,C =9.9 Hz), 53.6 (d, JP,C =6.8 Hz), 18.1 (d, JP,C =
3
1
Allyl phenyl(5-phenylpenta-2,4-diyn-1-yl)phosphinate (3i):
144.1 Hz); P NMR (CDCl , 162 MHz): d=22.5. HR-MS
3
1
+
Yield: 45.4 mg (71%); yellow liquid; H NMR (CDCl3,
(EI-TOF): m/z=266.0505, calcd. for C H O PF [M ]:
13
12
3
4
7
5
00 MHz): d=7.93–7.88 (m, 2H), 7.64–7.60 (m, 1H), 7.57–
.51 (m, 2H), 7.48–7.46 (m, 2H), 7.37–7.27 (m, 3H), 6.03–
.93 (m, 1H), 5.41 (dd, J =16.8 Hz, J =1.2 Hz, 1H), 5.41
266.0508.
Diphenyl(undeca-2,4-diyn-1-yl)phosphine oxide (3n):
Yield: 56.3 mg (81%); yellow liquid; H NMR (CDCl3,
1
1
2
(
dd, J =10.4 Hz, J =0.8 Hz, 1H), 4.70–4.64 (m, 1H), 4.54–
.47 (m, 1H), 3.22–3.04 (m, 2H); C NMR (CDCl3,
400 MHz): d=7.83–7.78 (m, 4H), 7.58–7.54 (m, 2H), 7.51–
7.47 (m, 4H), 3.35 (d, J=17.2 Hz, 2H), 2.21–2.18 (m, 2H),
1.50–1.42 (m, 2H), 1.36–1.21 (m, 6H), 0.86 (t, J=6.8 Hz,
1
2
1
3
4
1
7
1
1
7
5
00 MHz): d=133.0 (d, JP,C =2.2 Hz), 132.5, 132.4 (d, JP,C
.4 Hz), 131.9 (d, JP,C =9.8 Hz), 129.1, 128.7 (d, JP,C
32.8 Hz), 128.6 (d, JP,C =13.2 Hz), 128.3, 121.4 (d, JP,C
=
=
=
1
3
3H); C NMR (CDCl , 100 MHz): d=132.4 (d, J
=
3
P,C
3.0 Hz), 131.3 (d, JP,C =9.5 Hz), 130.9 (d, JP,C =101.6 Hz),
128.6 (d, JP,C =12.0 Hz), 79.5 (d, JP,C =3.3 Hz), 69.9 (d, JP,C
.4 Hz), 118.4, 75.9 (d, JP,C =3.6 Hz), 73.8 (d, JP,C =5.2 Hz),
3.7 (d, JP,C =12.2 Hz), 68.2 (d, JP,C =9.2 Hz), 65.9 (d, J
=
=
9.1 Hz), 66.8 (d, JP,C =11.4 Hz), 64.7 (d, JP,C =5.6 Hz), 31.2,
P,C
3
1
31
.3 Hz), 23.2 (d, JP,C =96.4 Hz);
P NMR (CDCl3,
28.4, 28.0, 23.3 (d, JP,C =68.8 Hz), 22.4, 19.1, 13.9; P NMR
Adv. Synth. Catal. 0000, 000, 0 – 0
7
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

UPDATES
asc.wiley-vch.de
(
3
CDCl3, 162 MHz): d=29.2; HR-MS (EI-TOF): m/z=
evacuated and backfilled with N2 (3 cycles). 1.0 mL of
DMSO was injected. The mixture was stirred at 608C over-
night. After the reaction was complete (monitored by TLC),
water was added. The mixture was extracted with EtOAc
(10 mL ꢂ 3 times). The combined organic layers were
washed with water, brine and dried with Na SO . Removal
+
48.1643, calcd. for C H OP [M ]: 348.1643.
23 25
Diethyl undeca-2,4-diyn-1-ylphosphonate (3o): Yield:
1
4
3.2 mg (76%); yellow liquid; H NMR (CDCl , 400 MHz):
3
d=4.21–4.14 (m, 4H), 2.81 (d, J=22.4 Hz, 2H), 2.45–2.40
(
6
3
m, 2H), 1.53–1.46 (m, 2H), 1.36–1.24 (m, 12H), 0.86 (t, J=
2
4
13
.8 Hz, 3H); C NMR (CDCl , 100 MHz): d=78.9 (d, J
=
P,C
of the solvent under vacuum left a slurry residue, which was
purified by flash chromatography on silica to afford the un-
3
.5 Hz), 67.8 (d, JP,C =9.7 Hz), 66.1 (d, JP,C =15.3 Hz), 64.8
(
d, JP,C =7.3 Hz), 63.0 (d, JP,C =6.7 Hz), 31.2, 28.4, 28.0, 22.4,
9.1, 18.6 (d, JP,C =144.5 Hz), 16.3 (d, JP,C =5.7 Hz), 13.9;
seperable mixture of 6a and 6b; yield: 50.7 mg (total: 68%).
1
1
H NMR (CDCl , 400 MHz): d=7.75–7.67 (m, 4H), 7.52–
3
31
P NMR (CDCl , 162 MHz): d=20.5; HR-MS (EI-TOF):
7.41 (m, 6H), 7.29–7.21 (m, 3H), 7.13–7.11 (m, 2H), 6.05 (s,
0.83H), 5.97 (d, J=2.0 Hz, 0.17H), 3.95 (s, 1.66H), 3.88 (s,
3
+
m/z=284.1545, calcd. for C H O P [M ]: 284.1541.
1
5
25
3
Allyl
phenyl(undeca-2,4-diyn-1-yl)phosphinate
(3p):
0.34H), 3.77 (s, J=14.0 Hz, 0.34H), 3.69 (d, J=13.2 Hz,
1
31
Yield: 48.5 mg (74%); yellow liquid; H NMR (CDCl3,
00 MHz): d=7.90–7.85 (m, 2H), 7.62–7.58 (m, 1H), 7.54–
.49 (m, 2H), 6.01–5.92 (m, 1H), 5.39 (dd, J =17.2 Hz, J =
.2 Hz, 1H), 5.26 (d, J=10.4 Hz, 1H), 4.67–4.61 (m, 1H),
1.66H); P NMR (CDCl , 162 MHz): d=28.1, 27.2; HR-MS
3
+
4
7
1
4
1
3
3
(ESI-TOF): m/z=374.1308, calcd. for C H NO P [MH ]:
2
3
21
2
374.1310.
1
2
.51–4.44 (m, 1H), 3.09–2.91 (m, 2H), 2.26–2.22 (m, 2H),
.54–1.47 (m, 2H), 1.39–1.24 (m, 6H), 0.89 (t, J=6.8 Hz, General Procedure for the Cyclization of Phosphoryl
1
3
H); C NMR (CDCl , 100 MHz): d=132.9 (d, J
=
P,C
1,3-Diynes 3 with Hydrazine
3
.0 Hz), 132.6 (d, JP,C =6.5 Hz), 132.0 (d, JP,C =9.5 Hz), 129.1
d, JP,C =131.5 Hz), 128.6 (d, JP,C =12.0 Hz), 118.2, 79.1 (d,
JP,C =3.7 Hz), 68.7 (d, JP,C =10.0 Hz), 66.5 (d, JP,C =12.8 Hz),
5.8 (d, JP,C =6.5 Hz), 64.9 (d, JP,C =6.6 Hz), 31.2, 28.4, 28.1,
2.9 (d, JP,C =96.9 Hz), 22.5, 19.2, 14.0; P NMR (CDCl3,
An oven-dried Schlenk tube containing a Teflon-coated stir
bar was charged with phosphoryl 1,3-diyne 3. The Schlenk
tube was sealed and then evacuated and backfilled with N2
(3 cycles). 1.0 mL of DMSO was injected, followed by the
injection of hydrazine (3.0 equiv., 80 wt% in water). The
mixture was stirred at 608C overnight. After the reaction
was complete (monitored by TLC), water was added. The
mixture was extracted with EtOAc (10 mLꢂ3). The com-
bined organic layers were washed with water, brine and
dried with Na SO . Removal of the solvent under vacuum
(
6
2
1
31
62 MHz): d=35.7; HR-MS (EI-TOF): m/z=328.1596,
calcd. for C H O P [M ]: 328.1592.
+
20
25
2
Procedure for the Olefination Reaction of Dimethyl
5-Phenylpenta-2,4-diyn-1-yl)phosphonate (3f) with 1-
Pyrenecarbaldehyde to Produce 1-(6-Phenylhexa-1-
en-3,5-diyn-1-yl)pyrene (5)
(
2
4
left a slurry residue, which was purified by flash chromatog-
raphy on silica (PE/EtOAc-1:3 v/v) to afford 7.
5
-Benzyl-3-[(diphenylphosphanyl)methyl]-1H-pyrazole
An oven-dried Schlenk tube containing a Teflon-coated stir
bar was charged with dimethyl (5-phenylpenta-2,4-diyn-1-
yl)phosphonate (124.0 mg, 0.5 mmol). The Schlenk tube was
sealed and then evacuated and backfilled with N (3 cycles).
.0 mL of dry THF were injected, and the solution was
cooled to À788C. A solution of LiHMDS (0.55 mmol, 1M
in THF) was then injected under stirring. The mixture was
stirred for 2 h at the same temperature. Then 1-pyrenecar-
baldehyde (57.5 mg, 0.25 mmol) dissolved in 2.0 mL of dry
THF was added dropwise. The reaction was slowly warmed
to room temperature, and stirred overnight. The reaction
(
5
7a): Prepared from 68.0 mg of 3a (0.2 mmol); yield:
0.6 mg (68%); white solid; mp 217–2188C; H NMR
1
(
CDCl , 400 MHz): d=7.70–7.65 (m, 4H), 7.51–7.47 (m,
3
2
2H), 7.41–7.37 (m, 4H), 7.26–7.16 (m, 3H), 7.09 (d, J=
3
6
2
3
1
3
.8 Hz, 2H), 5.79 (s, 1H), 3.88 (s, 2H), 3.67 (d, J=12.8 Hz,
13
H); C NMR (CDCl , 100 MHz): d=138.9, 131.9 (d, J
=
P,C
3
.4 Hz), 131.8 (d, JP,C =100.2 Hz), 131.0 (d, JP,C =9.2 Hz),
28.6, 128.4 (d, JP,C =5.7 Hz), 126.3, 105.3 (d, J =4.2 Hz),
P,C
31
3.2, 29.9 (d, JP,C =68.3 Hz); P NMR (CDCl , 162 MHz):
3
d=30.0; HR-MS (ESI-TOF): m/z=373.1459, calcd. for
+
C H N OP [MH ]: 373.1470.
2
3
22
2
was quenched with aqueous NH Cl, extracted with EtOAc
10 mLꢂ3). The combined organic layers were dried with
4
{[5-(4-Fluorobenzyl)-1H-pyrazol-3-yl]methyl}diphenyl-
phosphine oxide (7b): Prepared from 40.0 mg of 3k
(
Na SO . Removal of the solvent under vacuum left a slurry
2
4
(0.11 mmol); yield: 29.5 mg (69%); white solid; mp 214–
residue, which was purified by flash chromatography on
silica to afford the product 5; yield: 57.4 mg (65%).
H NMR (CDCl , 400 MHz): d=8.39 (d, J=9.2 Hz, 0.85H),
.31 (d, J=9.2 Hz, 0.15H), 8.27–8.01 (m, 9H), 7.57–7.55 (m,
.7H), 7.52–7.49 (m, 0.3H), 7.39–7.34 (m, 3H), 6.54 (d, J=
6.0 Hz, 0.85H), 6.17 (d, J=12.0 Hz, 0.15H); HR-MS (EI-
TOF): m/z=352.1257, calcd. for C H [M ]: 352.1252.
1
2
7
158C; H NMR (DMSO-d , 400 MHz): d=12.4 (br, 1H),
6
.81–7.76 (m, 4H), 7.56–7.47 (m, 6H), 7.12–7.05 (m, 4H),
1
3
5.59 (s, 1H), 3.80 (d, J=14.8 Hz, 2H), 3.78 (s, 2H);
8
1
1
13
C NMR (CDCl , 100 MHz): d=161.4 (d, J =243.1 Hz),
3
P,C
1
34.8 (d, JP,C =3.4 Hz), 131.9 (d, JP,C =2.2 Hz), 131.7 (d,
JP,C =100.4 Hz), 131.0 (d, JP,C =9.4 Hz), 129.9 (d, JP,C
8.0 Hz), 128.5 (d, JP,C =11.8 Hz), 115.0 (d, J =21.3 Hz),
=
+
2
8
16
P,C
3
1
1
1
05.1, 32.5, 29.7 (d, JP,C =68.0 Hz); P NMR (DMSO-d6,
62 MHz): d=26.8. HR-MS (ESI-TOF): m/z=391.1362,
Procedure for the Cyclization of 3a and Hydroxyl-
amine to Produce 6a and 6b
+
calcd. for C H N OPF [MH ]: 391.1376.
2
3
21
2
[
(5-Benzyl-1H-pyrazol-3-yl)methyl]di-p-tolylphosphine
An oven-dried Schlenk tube containing a Teflon-coated stir
oxide (7c): Prepared from 36.8 mg of 3b (0.1 mmol); yield:
28.5 mg (71%); white solid; mp 228–2298C; H NMR
1
bar was charged with 3a (68.0 mg, 0.2 mmol), K CO
2
3
(
82.8 mg, 0.6 mmol) and hydroxylamine hydrochloride
(DMSO-d , 400 MHz): d=12.4 (br, 1H), 7.66–7.62 (m, 4H),
6
(
41.4 mg, 0.6 mmol). The Schlenk tube was sealed and then
7.27–7.22 (m, 6H), 7.19–7.15 (m, 1H), 7.09 (d, J=6.8 Hz,
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2
2
1
9
1
2
1
H), 5.62 (s, 1H), 3.80 (s, 2H), 3.74 (s, J=13.6 Hz, 2H),
Khemchyan, I. P. Beletskaya, Synlett 2009, 2375; g) V. P.
Ananikov, L. L. Khemchyan, I. P. Beletskaya, Russ. J.
Org. Chem. 2010, 46, 1269; h) I. G. Trostyanskaya, I. P.
Beletskaya, Tetrahedron 2014, 70, 2556; i) A. Duraud,
M. Toffano, J.-C. Fiaud, Eur. J. Org. Chem. 2009, 4400.
[4] a) Y. Gao, G. Wang, L. Chen, P. Xu, Y. Zhao, Y. Zhou,
L.-B. Han, J. Am. Chem. Soc. 2009, 131, 7956; b) Y.
Moglie, E. Mascarꢄ, V. Gutierrez, F. Alonso, G. Radi-
voy, J. Org. Chem. 2016, 81, 1813; c) P. Liu, J. Yang, P.
Li, L. Wang, Appl. Organomet. Chem. 2011, 25, 830;
d) J. Yang, T. Chen, Y. Zhou, S. Yin, L.-B. Han, Chem.
Commun. 2015, 51, 3549; e) J. Yang, T. Chen, Y. Zhou,
S.-F. Yin, L.-B. Han, Organometallics 2015, 34, 5095;
f) K. Jouvin, J. Heimburger, G. Evano, Chem. Sci. 2012,
3, 756; g) J. Hu, N. Zhao, B. Yang, G. Wang, L.-N. Guo,
Y.-M. Liang, S.-D. Yang, Chem. Eur. J. 2011, 17, 5516;
h) T. Wang, S. Chen, A. Shao, M. Gao, Y. Huang, A.
Lei, Org. Lett. 2015, 17, 118.
13
.31 (s, 6H); C NMR (CDCl , 100 MHz): d=147.5 (br),
3
42.2 (d, JP,C =2.4 Hz), 139.1, 138.3 (br), 131.0 (d, JP,C
=
.1 Hz), 129.2 (d, JP,C =12.8 Hz), 128.6 (d, JP,C =99.9 Hz),
28.4 (d, JP,C =29.8 Hz), 126.1, 105.1 (d, J =4.2 Hz), 33.3,
P,C
3
1
9.9 (d, JP,C =67.8 Hz), 21.5;
P NMR (DMSO-d6,
62 MHz): d=27.0; HR-MS (ESI-TOF): m/z=401.1779,
+
calcd. for C H N OP [MH ]: 401.1783.
25
26
2
[
(5-Benzyl-1H-pyrazol-3-yl)methyl]bis(4-fluorophenyl)-
phosphine oxide (7d): Prepared from 37.6 mg of 3d
0.1 mmol); yield: 25.0 mg (61%); white solid; mp 212–
(
1
2
7
7
3
138C; H NMR (DMSO-d , 400 MHz): d=12.4 (br, 1H),
.88–7.82 (m, 4H), 7.36–7.32 (m, 4H), 7.27–7.17 (m, 3H),
.09–7.07 (m, 2H), 5.62 (s, 1H), 3.83 (d, J=14.8 Hz, 2H),
.81 (s, 2H); C NMR (CDCl , 100 MHz): d=165.0 (dd,
6
13
3
JF,C =252.6 Hz, JP,C =2.7 Hz), 138.6, 133.5 (dd, JF,C =10.6 Hz,
JP,C =9.5 Hz), 128.5, 128.4, 127.5 (d, JP,C =103.9 Hz), 126.4,
1
15.9 (d, JF,C =21.6 Hz, J =12.6 Hz), 105.3, 33.0, 29.7 (d,
P,C
31
JP,C =69.7 Hz); P NMR (DMSO-d , 162 MHz): d=26.1;
6
[5] L.-B. Han, Y. Ono, H. Yazawa, Org. Lett. 2009, 11, 709.
HR-MS
(ESI-TOF):
m/z=409.1274,
calcd.
for
[
6] For other synthetic methods, see: a) Y.-Z. Chen, L.
+
C H N OPF [MH ]: 409.1281.
23
20
2
2
Zhang, A.-M. Lu, F. Yang, L. Wu, J. Org. Chem. 2015,
8
0, 673; b) T. Liu, J. Dong, S. J. Cao, L. C. Guo, L. Wu,
RSC Adv. 2014, 4, 61722; c) T. Liu, Y.-T. Xia, J. Zhu,
A.-M. Lu, L. Wu, Tetrahedron Lett. 2015, 56, 6508;
d) K. Komeyama, T. Kawabata, K, Takehira, K.
Takaki, J. Org. Chem. 2005, 70, 7260; e) Y. Kobayashi,
A. D. William, Org. Lett. 2002, 4, 4241; f) Y. Kobayashi,
A. D. William, Adv. Synth. Catal. 2004, 346, 1749;
g) A. L. Braga, C. R. B. Rhoden, G. Zeni, C. C. Silveira,
L. H. Andrade, J. Organomet. Chem. 2003, 682, 35.
Acknowledgements
Financial support from the National Natural Science Founda-
tion of China (21302095), Research Fund for the Doctoral
Program of Higher Education of China (20133221120003),
Jiangsu Provincial NSFC (BK20130924) and Foundation of
Jiangsu Educational Committee of China (13KJB150019) is
acknowledged. Ruwei Shen thanks Prof. Luling Wu of Zhe-
jiang University for the long-term support on his work.
[7] For selected examples on synthetic applications of
phosphonyl 1,3-dienes, see: a) C. E. Griffin, W. M.
Daniewski, J. Org. Chem. 1970, 35, 1691; b) S. D. Dar-
ling, N. Subramanian, J. Org. Chem. 1975, 40, 2851;
c) Z.-F. Xi, W.-X. Zhang, Z.-Y. Song, W.-X. Zheng, F.-
Z. Kong, T. Takahashi, J. Org. Chem. 2005, 70, 8785;
d) A. Azab, A. Quntar, T. Antebi, M. Srebnik, Hetero-
cycles 2010, 82, 417; e) E. Villemin, K. Robeyns, R. Ro-
biette, M.-F. Herent, J. Marchand-Brynaert, Tetrahe-
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8] a) R. Shen, B. Luo, J. Yang, L. Zhang, L.-B. Han,
Chem. Commun. 2016, 52, 6451; b) J. Yang, T. Chen,
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account: Q. Xu, L.-B. Han, J. Organomet. Chem. 2011,
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11] CCDC 1422251 contains the crystallographic data of
a. These data can be obtained free of charge from The
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lographic data of 6a and 7a, respectively. These data
can be obtained free of charge from The Cambridge
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data_request/cif.
[
13] In contrast, the allene–alkyne isomerization proceeds
rather slowly and hardly reaches full conversion in the
reactions of 1-phenylpropargyl acetate and diethyl
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[8a]
phosphonate (also see ref. ). Some results are shown
below.
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Copper-Catalyzed Allenylation-Isomerization Sequence of
Penta-1,4-diyn-3-yl Acetates with P(O)H Compounds:
Facile Synthesis of 1-Phosphonyl 2,4-Diynes
11
Adv. Synth. Catal. 2016, 358, 1 – 11
Ruwei Shen,* Jianlin Yang, Bing Luo, Lixiong Zhang,
Li-Biao Han*
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These are not the final page numbers!