Radical Hydrophosphorylation of Alkynes with R2P(O)H Generating Alkenylphosphine Oxides: Scope and Limitations

Article abstract of DOI:10.1021/acs.joc.8b01042

Radical hydrophosphorylation of aliphatic terminal alkynes with H-phosphine oxides can produce the corresponding anti-Markovnikov alkenylphosphorus adducts in moderate yields. This method is a cleaner approach for the preparation of the corresponding alke

Full text of DOI:10.1021/acs.joc.8b01042

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Note
Radical hydrophosphorylation of alkynes with R2P(O)H
generating alkenylphosphine oxides: scope and limitations
Tianzeng Huang, Yuta Saga, Haiqing Guo, Aya Yoshimura, Akiya Ogawa, and Li-Biao Han
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b01042 • Publication Date (Web): 21 Jun 2018
Downloaded from http://pubs.acs.org on June 22, 2018
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Radical hydrophosphorylation of alkynes with R P(O)H generating
2
alkenylphosphine oxides: scope and limitations
a,b
a
a
c
d*
a,b*
Tianzeng Huang, Yuta Saga, Haiqing Guo, Aya Yoshimura, Akiya Ogawa, LiꢀBiao Han
a
1
1
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National Institute of Advanced Industrial Science and Technology (AIST), 1ꢀ1ꢀ1, Higashi, Tsukuba, Ibaraki, 305ꢀ8565,
Japan.
b
Division of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305ꢀ8571, Japan
c
Department of Applied Chemistry, Graduate School of Science and Engineering, Ehime University, 3 Bunkyoꢀcho,
Matsuyama, Ehime 790ꢀ8577, Japan
d
Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1ꢀ1 Gakuenꢀcho,
Nakaku, Sakai, Osaka 599ꢀ8531, Japan
ABSTRACT
Radical hydrophosphorylation of aliphatic terminal alkynes with Hꢀphosphine oxides can produce the
corresponding antiꢀMarkovnikov alkenylphosphorus adducts in moderate yields. This method is a cleaner way for
the preparation of the corresponding alkenylphosphine oxides since it avoids the use of a metalꢀcatalyst that
sometimes is difficult to remove from the products.
Organophosphorous compounds are of high importance in organic synthesis, biochemistry and material
1
sciencies. The metalꢀcatalyzed addition of a hydrogen phosphoryl compound P(O)H to an alkyne
(
hydrophosphorylation) is a powerful method for the preparation of an alkenylphosphoryl compound which is
2
highly useful but difficult to prepare by the conventional method (Scheme 1). One of the remarkable features of
this method is the nearly perfect controllable regioꢀ and stereoselectivity of the addition products, i.e., both the
2b
αꢀadduct and the βꢀadduct can be highly selectively generated, respectively, by employing the right catalyst.
However, despite its novelty, still there are few drawbacks associated with the metalꢀcatalyzed
hydrophoshorylations. One of such drawbacks is the difficult removal of the metalꢀcatalyst from the products
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because of the strong coordination of the P(O) products to the metals. As a result, the products prepared by the
metalꢀcatalyzed hydrophosphorylation, that inherently are colorless oil or white solid when pure, often are
yellowish due to the contamination of the metals. This metalꢀcontamination problem can hamper their application
as starting materials to electronical materials and pharmaceuticals since “metalꢀfree” clean chemicals are usually
required.
0
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Scheme 1 Metal-catalyzed addition of P(O)H compounds to alkynes.
Radicalꢀinitiated additions (especially those of the photoꢀinduced ones) of P(O)H compounds to alkynes can
avoid the aboveꢀmentioned metalꢀcontamination problem. From the literatures, it is expected that both a radical
4
initiator (including oxygen) and light should possibly induce this kind of radical hydrophosphorylation. However,
such studies are rather limited, and the scope and limitations of such a radical hydrophosphorylation are not clear.
4g
Thus, Russian chemists reported the radical addition of R P(O)H to alkynes initiated by dibenzoyl peroxide.
2
However, the yield was low (ca. 24% yield). Recently, the hydrophosphorylation of terminal alkynes with
(
MeO) P(O)H was conducted under photoꢀirradiation in the presence of 0.2~0.5 equiv.
2
4
aꢀb
2
2
,2ꢀdimethoxyꢀ2ꢀphenylacetophenone (DPAP) as an initiator. However, a large excess amount of (MeO) P(O)H
(100 equivs) had to be used.
2
b,5
In conjunction with our studies on metalꢀmediated hydrophosphorylation, we feel it is necessary to have a
4b
proper assessment of the radical hydrophosphorylation reactions of alkynes with P(O)H compounds. Herein we
report our studies on the photoꢀirradiated and radical initiatorꢀinduced additions of Hꢀphosphine oxides and related
compounds to alkynes (eq 1). As described below, though, in general, far less efficient than that of the
metalꢀmediated hydrophosphorylations, the combination of terminal aliphatic alkynes and Hꢀphosphine oxides can
produce the βꢀadducts selectively in moderate to good yields. In particular, propargylic alcohols that could not be
5
used in the palladiumꢀmediated hydrophosphorylations are also applicable.
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Light-induced addition of P(O)H compounds to alkynes.
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As shown in Table 1, a mixture of 1ꢀoctyne 1a and Ph P(O)H 2a was placed in a Pyrex glass tube under nitrogen
2
atmosphere and irradiated using a highꢀpressure Hg lamp for 4 h. In the absence of a solvent, an equimolar mixture
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
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9
0
of 1a and 2a produced 49% yield of 3a as a Zꢀ and Eꢀisomer mixture (Z/E = 67/33) (run 1). However, a side
7
product 4a by the double addition of 2a to 1a was also generated in 15% yield based on 2a. By employing 2
equivs of 2a, the yield of 3a increased to 61% (run 2), albeit 4a also increased to 29% yield. On the other hand, an
excess 1a suppressed the formation of 4a (runs 3 and 4), although too much of 1a lowered the yield of 3a (run 4).
The reaction took place more cleanly in a solvent (runs 5ꢀ16) since the formation of 4a could be suppressed.
Among the solvents investigated, iꢀPrOH was chosen as the solvent considering both yields and selectivity. As
shown in run 11, 70% yield of 3a (Z/E = 73/27) could be obtained by using iꢀPrOH as the solvent.
a
Table 1. Addition of Ph
2
P(O)H to 1-octyne under photo-irradiation.
b
c
run 1a (mmol) 2a (mmol) solvent 3a yield (%) (Z/E) 4a yield (%)
1
2
3
4
0.1
0.1
0.2
0.5
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.2
none
none
none
none
THF
THF
THF
THF
49 (67/33)
61 (61/39)
61(69/31)
54(70/30)
51 (66/34)
62 (65/35)
68 (62/38)
68 (60/40)
63 (68/32)
61 (54/45)
70 (73/27)
15
29
0.1
10
0.1
trace
trace
trace
trace
trace
trace
trace
trace
d
5
6
0.1
e
0.12
0.12
0.12
0.12
0.12
0.12
7
f
8
9
CH Cl2
2
1
0
6 6
C H
11
iꢀPrOH
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5
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6
1
1
1
1
2
3
4
5
0.2
0.1
0.1
0.1
0.1
0.1
iꢀPrOH
iꢀPrOH
EtOH
47 (75/25)
76 (71/29)
47 (80/20)
58 (80/20)
42 (58/42)
trace
8
0.15
0.12
0.12
0.12
trace
trace
trace
tꢀBuOH
iꢀPrOH
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
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7
8
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0
1
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2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
g
16
a
Reactions conditions: a mixture of 1a and 2a was sealed in a Pyrexꢀtube under dry nitrogen atmosphere and
6
irradiated using a highꢀpressure Hg lamp (Ushio, SXꢀU1501HQ). Yield was calculated based on the less employed
b
c
starting material. The yield of 3a and the Z/E ratio were determined by GC. The yield of 4a was calculated from
31
d
e
f
g
P NMR spectroscopies. 3 h. 2 h. 6 h. Sealed under air atmosphere.
As shown in Table 2, a variety of alkynes was used to carry out the photoꢀirradiated additions. Similar to
1
ꢀoctyne, terminal aliphatic alkynes with an ester group (run 3) or a hydroxyl group (run 4) could react to give the
corresponding adducts in good yields. Alkynes with chloro (run 2) group, however, gave low yields of the products.
The bulky tꢀbutylacetylene (run 5) also produced the corresponding adducts, albeit with the Eꢀisomer as the major
product due to steric reasons (vide infra). A conjugated alkyne (run 6), phenylacetylene (run 7) and internal alkyne
8
(
run 16), however, hardly produced the adducts, and most of Ph
2
P(O)H remained unreacted. Remarkably, however,
the very bulky silylacetylenes (runs 8 and 9) and propargyl alcohols (runs 10ꢀ15) all gave the adducts in good
yields. An interesting phenomenon is that, being different from tꢀbutylacetylene (run 5), both the bulky
3
silylacetylenes and proparlgyl alcohols, all give the Zꢀadduct as the major stereomer, indicating that the R Si and
OH groups significantly contribute to the reactions (vide infra). The efficient reactions with these cheap propargyl
alcohols are practically important. Moreover, they are also novel because similar additions by the
5
palladiumꢀcatalyzed hydrophosphorylation hardly took place. As expected, under similar conditions, the reaction
conducted at 1 mmol scale gave similar results. For example, a mixture of Ph
2
P(O)H (242.6 mg, 1.2 mmol) and
2ꢀmethylꢀ3ꢀbutynꢀ2ꢀol (84.1 mg, 1.0 mmol) in iꢀPrOH (1 mL) under photoꢀirradiation for 4 h gave 76% yield (Z/E
=
2 2
77/23) of 3m after purification using short column chromatography on silica gel (eluent CH Cl /MeOH = 100/1).
a
2
Table 2. Photo-induced addition of Ph P(O)H to alkynes.
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b
c
run
1
alkyne
product yield (%) (Z/E)
3a
3b
3c
3d
3e
65 (73/27)
33 (55/45)
54 (64/36)
71 (70/30)
42 (37/63)
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2
3
4
5
6
7
3f
trace
3g
3h
3i
trace
d
8
36 (53/47)
81 (87/13)
45 (60/40)
9
1
0
1
3j
1
3k
3l
66 (71/29)
84 (72/28)
81 (72/28)
88 (59/41)
1
1
2
3
3m
3n
14
15
3o
3p
70 (70/30)
no addition
1
6
a
Reaction conditions: a iꢀPrOH solution of an alkyne and Ph
2
P(O)H in a Pyrexꢀtube was irradiated using a
highꢀpressure Hg lamp (Ushio, SXꢀU1501HQ). The products were isolated using a recycling preparative HPLC
b
c
(
JAI) equipped with a 1H and 2H GPC columns using CHCl
3
. Isolated yield. The Z/E ratio was determined for the
3
1
d
crude mixture by GC or P NMR. Ca. 25% of Ph
2
P(O)CH
2
CH P(O)Ph was detected, which was generated by the
2
2
desilylation of 3i followed by the addition of Ph P(O)H.
2
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As shown in eq 2, as expected, the addition reaction did not proceed in the presence of a radical scavenger
4
h
TEMPO. A possible mechanism for this photoꢀinduced hydrophosphorylnation is shown in Scheme 2. The
4
phosphoryl radical generated under light adds to alkynes to generate alkenyl radicals which exists in trans I and
0
1
2
3
4
5
6
7
8
9
0
1
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9
0
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0
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cis II forms with the former being more stable but less reactive and the latter being more reactive but less stable.
2
Subsequent reactions of I and II with Ph P(O)H give the corresponding alkenylphosphine oxides. The Z/E ratio of
the adducts reflects the result of reactions of I and II. Since II is more reactive, usually Zꢀadduct was generated as
the major product. However, if R is too bulky (tꢀBu, for example), the vinyl radical might predominantly exist in
the trans form I, which consequently generates the Eꢀadduct as the major isomer. As shown in Scheme 2, it was
expected that a silyl group and OH group could interact with the phosphoryl group to stabilize the cisꢀradical II.
Therefore, different from tꢀbutylacetylene, Zꢀadducts were generated from these bulky alkynes.
2
Scheme 2 A possible mechanism for the photo-induced addition of Ph P(O)H to alkynes.
Under similar conditions, the reactions of other [P]H compounds were investigated (Table 3). The bulky
Ph(tꢀBu)P(O)H (run 1) also produced the corresponding adducts in 45% yield. Aliphatic phosphine oxides (runs 2
and 3) reacted similarly. Ph(EtO)P(O)H could also produce the corresponding adducts. However, additions with
(
EtO) P(O)H hardly proceeded. Therefore, the reactivity of P(O)H compounds roughly follow a decreasing order of
2
2
Hꢀphosphine oxide > Hꢀphosphinate > Hꢀphosphonate. Finally, diphenylphosphine Ph PH could also be used as the
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substrate to produce the corresponding alkenylphosphine in good yields (run 6).
a
Table 3. Light-induced addition of P(O)H compounds to 1-octyne.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
b
c
run
1
[P]H
product yield (%) (Z/E)
Ph(tꢀBu)P(O)H
3q
3r
3s
3t
45 (77/23)
66 (36/64)
61 (50/50)
48 (62/38)
trace
2
2 4 2
[Ph(CH ) ] P(O)H
3
Cy P(O)H
2
4
Ph(EtO)P(O)H
5
(EtO) P(O)H
3u
3v
2
b
6
Ph
2
PH
67 (57/43)
a
b
c
Reaction was similarly carried out and the products were isolated as described in Table 2. Isolated yield. The
31
d
31
Z/E ratio was determined for the crude mixture by P NMR. Calculated based on P NMR after 8 h irradiation
with a xenon lamp. Isolated as its corresponding Ph P(O) compounds by oxidation with H O .
2
2
2
4
h
Finally, since photoꢀinitiated addition of Ph P(O)H to terminal olefins also took place, to compare the reactivity
2
2
of a double bond with a triple bond, we carried out a competing reaction of Ph P(O)H (0.1 mmol) between 1ꢀoctene
(0.1 mmol) and 1ꢀoctyne (0.1 mmol) (eq 3). As determined by NMR, the ratio of the products from 1ꢀoctene 5 vs
that from 1ꢀoctyne 3a was 63/37, indicating that an olefin is more reactive (ca. two times faster) than an alkyne.
Radical-initiator-induced addition of P(O)H compounds to alkynes.
As shown in Table 4, Ph P(O)H can add to 1ꢀoctyne in the presence of a radical initiator. Thus, a mixture of the
2
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o
10
two reagents in benzene on heating at 70 C in the presence of 10 mol% AIBN produced a mixture of the
monoꢀaddition product 3a and the double addition product 4a in 43% and 29% yields, respectively (run 1). The
reaction also took place in THF, although the yield of the double addition product 4a slightly increased (run 2). The
formation 4a could be negligible by carrying out the reaction in a more diluted solution (runs 3 and 4) or at lower
temperatures (runs 5 and 6). Interestingly, the Z/E selectivity of 3a could be over 8/2 when carrying out the reaction
in EtOH, although the yields were low (runs 7, 8). By conducting the reaction using a radical initiator that
0
1
2
3
4
5
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8
9
0
1
2
3
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0
1
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7
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0
1
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0
1
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8
9
0
1
0
decomposes at a low temperature Vꢀ70 [2,2’ꢀazobis(4ꢀmethoxyꢀ2,4ꢀdimethylvaleronitrile)], moderate yields of 3a
could be generated selectively (runs 9ꢀ11). Moreover, with 20% of an initiator Vꢀ601 [dimethyl
10
2
,2’ꢀazobis(isobutyrate)] , moderate yields of 3a with high Z/E selectivities could also be generated (runs 13ꢀ16).
4d
Since air can initiate the radical addition of P(O)H compounds, as expected, 58% yield of 3a could also be
generated by conducting the reaction under air (run 17).
a
Table 4. Addition of Ph P(O)H to 1-octyne induced by a radical initiator.
2
o
b
c
run
solvent temp. ( C) 3a yield (%) (Z/E) 4a yield (%)
d
1
C
6
H
6
70
70
70
70
50
35
70
50
35
43 (69/31)
58(67/33)
70(67/33)
55(66/34)
53(71/29)
16(70/30)
36(82/18)
15(84/16)
49(71/29)
29
d
2
THF
THF
THF
THF
THF
EtOH
EtOH
THF
36
d,e
3
20
d,f
4
trace
trace
trace
trace
trace
trace
d
5
d
6
d
7
d
8
g
9
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g
1
0
THF
THF
50
35
50
50
50
50
50
50
52(73/27)
59(72/28)
17(88/12)
60(80/20)
47(82/18)
45(85/15)
66 (86/14)
58(89/11)
trace
trace
trace
trace
trace
trace
trace
trace
g, h
g
11
1
1
2
EtOH
i
i
i
j
3
EtOH
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
14
15
16
iꢀPrOH
tꢀBuOH
tꢀBuOH
EtOH
k
1
7
a
Reactions conditions: a mixture of 1a (0.2 mmol), 2a (0.1 mmol), a radical initiator and a solvent (0.2 mL) was
b
sealed in a Pyrexꢀtube (1 mL) under nitrogen atmosphere and heated overnight. The yield of 3a based on 2a and
c
31
the Z/E ratio were determined from crude mixture by GC. The yield of 4a based on 2a was estimated from
P
d
e
f
g
h
i
j
k
NMR. 10 mol% AIBN. 0.3 mL. 0.5 mL. 10 mol% Vꢀ70. 1a (0.1 mmol). 20 mol% Vꢀ601. 40 mol% Vꢀ601. The
Pyrex tube was sealed with air.
However, similar to the photoꢀinduced radical addition described above, this radicalꢀinitiatorꢀinduced addition
8
,11
does not apply to phenylacetylenes and other conjugate alkynes related.
RO) P(O)H were also hardly applicable to this reaction.
In conclusion, the radical hydrophosphorylation of alkynes with P(O)H compounds by photoꢀirradiation or
radicalꢀinitiators have been studied. It appears that hydrogen phosphonates (RO) P(O)H and conjugated alkynes
are not applicable to this reaction. However, with the combination of Hꢀphosphine oxides R P(O)H and aliphatic
Furthermore, hydrogen phosphonates
(
2
2
2
terminal alkynes, moderate yields of the antiꢀMarcovnikov alkenylphosphine oxides could be generated. In
5
particular, propargyl alcohols, which are not applicable to the palladiumꢀcatalyzed hydrophosphorylations, can
give the corresponding adducts in good yields. Therefore, this metalꢀfree clean radical hydrophosphorylation can
serve, to some extent, as a complimentary to the metalꢀmediated hydrophosphorylation of alkynes.
EXPERIMENTAL SECTION
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1
General information: All materials were purchased and used without further purification. H NMR spectra were
1
3
recorded on a JEOL JNMꢀECS400 (400 MHz) FT NMR system in CDCl
NMR spectra were taken on a JEOL JNMꢀECS400 (100 MHz) FT NMR system in CDCl3. P NMR spectra were
taken on a JEOL JNMꢀECX400 (162 MHz) FT NMR system in CDCl with 85% H PO solution as an external
standard. Isolation using a preparative HPLC (recycle GPC) was performed on a Japan Analytical Industry LCꢀ908
equipped with JAIGELꢀ1H and JAIGELꢀ2H columns using CHCl . The Zꢀ and Eꢀisomer configuration of the
3 4
with Me Si as an internal standard. C
3
1
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3
3
4
3
1
compounds was assigned on the basis of HꢀNMR spectra by comparing with the reported data and/or the coupling
constants of the vinyl protons (JHH and JHP).
General procedures: a mixture of 1 and 2 in a solvent (or neat) was sealed in a Pyrexꢀtube and was irradiated
using a highꢀpressure Hg lamp (Ushio, SXꢀU1501HQ) (Tables 1, 2 and 3). Similarly, were conducted
radicalꢀinitiated additions except a radical initiator or air was added to the reaction mixture instead of
photoꢀirradiation (Table 4).
12
o
1
(
Z)-oct-1-en-1-yldiphenylphosphine oxide [3a (Z)]. White solid; mp 66ꢀ67 C. HꢀNMR (400 MHz, CDCl ):
3
δ (ppm) 7.75~7.69 (m, 4H), 7.49~7.39 (m, 6H), 6.66 (ddt, J
1 2 3 1
= 7.6 Hz, J = 12.8 Hz, J = 40.4 Hz, 1H), 6.08 (ddt, J
= 1.6 Hz, J = 12.8 Hz, J = 25.6 Hz, 1H), 2.54 ~2.48 (m, 2H), 1.36~1.28 (m, 2H), 1.23~1.09 (m, 6H), 0.81 (t, J =
2
3
1
3
6
3
.8 Hz, 3H). CꢀNMR (100 MHz, CDCl ): δ (ppm) 155.2, 134.7 (d, J = 103.0 Hz), 131.5 (d, J = 2.9 Hz), 130.9 (d,
J = 9.5 Hz), 128.5 (d, J = 11.4 Hz), 121.3 (d, J = 100.1 Hz), 31.6, 31.0 (d, J = 8.5 Hz), 28.9, 28.8, 22.5, 14.1.
31
3
PꢀNMR (162 MHz, CDCl ): δ (ppm) 21.7.
13
o
1
(
E)-oct-1-en-1-yldiphenylphosphine oxide [3a (E)]. White solid; mp 69ꢀ70 C. HꢀNMR (400 MHz, CDCl ):
3
δ (ppm) 7.70~7.64 (m, 4H), 7.52~7.41 (m, 6H), 6.71 (ddt, J
1
= 6.8 Hz, J
2
= 16.8 Hz, J
3
= 19.6 Hz, 1H), 6.20 (ddt, J
1
=
1.6 Hz, J = 16.8 Hz, J = 24.8 Hz, 1H), 2.31~2.25 (m, 2H), 1.50~1.42 (m, 2H), 1.34~1.20 (m, 6H), 0.86 (t, J =
2 3
1
3
6
.8 Hz, 3H). CꢀNMR (100 MHz, CDCl
3
): δ (ppm) 153.0, 133.3 (d, J = 103.9 Hz), 131.7 (d, J = 2.8 Hz), 131.3 (d,
J = 9.5 Hz), 128.5 (d, J = 12.4 Hz), 121.6 (d, J = 102.9 Hz), 34.6 (d, J = 16.2 Hz), 31.6, 28.9, 27.9, 22.6, 14.1.
31
3
PꢀNMR (162 MHz, CDCl ): δ (ppm) 24.3.
1
(
Z)-(6-chlorohex-1-en-1-yl)diphenylphosphine oxide [3b (Z)]. White viscous tar. HꢀNMR (400 MHz, CDCl ):
3
δ (ppm) 7.73~7.68 (m, 4H), 7.50~7.41 (m, 6H), 6.65 (ddt, J
1
= 6.8 Hz, J
2
= 13.2 Hz, J
3
= 40.4 Hz, 1H), 6.13 (dd, J
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=
13.2 Hz, J = 25.2 Hz, 1H), 3.44 (t, J = 6.8 Hz, 2H), 2.61~2.56 (m, 2H), 1.71~1.64 (m, 2H), 1.55~1.47 (m, 2H).
2
13
3
CꢀNMR (100 MHz, CDCl ): δ (ppm) 154.0, 134.4 (d, J = 103.9 Hz), 131.6 (d, J = 1.9 Hz), 130.9 (d, J = 9.5 Hz),
3
1
128.6 (d, J = 12.3 Hz), 122.2 (d, J = 100.0 Hz), 44.8, 31.9, 29.9 (d, J = 8.5 Hz), 26.1. PꢀNMR (162 MHz, CDCl ):
3
+
37
+ 35
δ (ppm) 21.8. GCꢀMS (EI, 70 eV) m/z = 320 (M , Cl, 6), 318 (M , Cl, 18). Anal. Calcd for C18H20ClOP: C,
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
67.82; H, 6.32. Found: C, 67.60; H, 6.30.
o
1
(E)-(6-chlorohex-1-en-1-yl)diphenylphosphine oxide [3b (E)]. White solid; mp 80ꢀ82 C. HꢀNMR (400 MHz,
CDCl ): δ (ppm) 7.69~7.63 (m, 4H), 7.51~7.40 (m, 6H), 6.70 (ddt, J = 6.4 Hz, J = 16.8 Hz, J = 19.6 Hz, 1H),
3
1
2
3
6
1
1
.24 (dd, J
1
2
= 16.8 Hz, J = 24.4 Hz, 1H), 3.51 (t, J = 6.4 Hz, 2H), 2.34~2.29 (m, 2H), 1.82~1.75 (m, 2H),
13
.67~1.59 (m, 2H). CꢀNMR (100 MHz, CDCl ): δ (ppm) 151.6, 133.1 (d, J = 104.8 Hz), 131.8 (d, J = 1.9 Hz),
3
31.3 (d, J = 10.5 Hz), 128.5 (d, J = 11.5 Hz), 122.4 (d, J = 101.9 Hz), 44.6, 33.6 (d, J = 16.2 Hz), 32.0, 25.2.
31
+
37
+ 35
PꢀNMR (162 MHz, CDCl ): δ (ppm) 24.0. GCꢀMS (EI, 70 eV) m/z = 320 (M , Cl, 4), 318 (M , Cl, 11). Anal.
3
Calcd for C18
H20ClOP: C, 67.82; H, 6.32. Found: C, 67.74; H, 6.33.
13
1
4
-(Diphenylphosphoryl)but-3-en-1-yl pivalate [3c (E + Z)]. White solid. HꢀNMR (400 MHz, CDCl ): δ
3
(ppm) 7.72~7.63 (m, 4H, E + Z), 7.50~7.41 (m, 6H, E + Z), 6.76~6.59 (m, 1H, E + Z), 6.32 (dd, J
1 2
= 17.2 Hz, J =
23.6 Hz, 1H, E), 6.19 (dd, J = 13.2 Hz, J = 25.6 Hz, 1H, Z), 4.18 (t, J = 6.4 Hz, 2H, E), 4.09 (t, J = 6.4 Hz, 2H, Z),
1
2
13
3
.03~2.98 (m, 2H, Z), 2.64~2.59 (m, 2H, E), 1.13 (s, 9H, Z), 1.09 (s, 9H, E). CꢀNMR (100 MHz, CDCl
3
): δ (ppm)
178.4 (Z), 178.3 (E), 149.6 (Z), 147.6 (E), 134.0 (d, J = 103.9 Hz, Z), 132.7 (d, J = 104.9 Hz, E) 131.8 (d, J = 2.8
Hz, E), 131.7 (d, J = 2.8 Hz, Z), 131.2 (d, J = 10.5 Hz, E), 130.9 (d, J = 9.6 Hz, Z), 128.6 (d, J = 12.4 Hz, Z), 128.5
(d, J = 11.4 Hz, E), 124.5 (d, J = 101.1 Hz, E), 124.2 (d, J = 98.2 Hz, Z), 63.0 (Z), 62.0 (E), 38.70 (Z), 38.67 (E),
3
1
33.6 (d, J = 17.1 Hz, E), 29.8 (d, J = 7.7 Hz, Z), 27.14 (Z), 27.08 (E). PꢀNMR (162 MHz, CDCl
3
): δ (ppm) 23.8
(
E), 22.2 (Z).
o
1
(
Z)-(6-hydroxyhex-1-en-1-yl)diphenylphosphine oxide [3d (Z)]. White solid; mp 94ꢀ96 C. HꢀNMR (400
MHz, CDCl ): δ (ppm) 7.73~7.68 (m, 4H), 7.51~7.40 (m, 6H), 6.75 (ddt, J = 6.4 Hz, J = 12.8 Hz, J = 40.4 Hz,
3
1
2
3
1 2
1H), 6.10 (dd, J = 12.8 Hz, J = 26.4 Hz, 1H), 3.60 (t, J = 6.4 Hz, 2H), 2.56~2.51 (m, 2H), 2.44 (b, 1H), 1.59~1.48
13
(
m, 4H). CꢀNMR (100 MHz, CDCl ): δ (ppm) 154.9, 134.3 (d, J = 103.9 Hz), 131.6 (d, J = 1.9 Hz), 130.9 (d, J =
3
31
9
.5 Hz), 128.6 (d, J = 11.5 Hz), 121.5 (d, J = 100.1 Hz), 61.4, 31.3, 29.9 (d, J = 7.6 Hz), 25.3. P NMR (162 MHz,
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1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
+
+
CDCl ): δ (ppm) 22.5. MS (EI, 70 eV) m/z = 301 ([M+H] , 5), 300 (M , 24). Anal. Calcd for C H O P: C, 71.98;
3
18 21
2
H, 7.05. Found: C, 71.84; H, 7.04.
1
4
o
1
(
E)-(6-hydroxyhex-1-en-1-yl)diphenylphosphine oxide [3d (E)]. White solid; mp 66ꢀ68 C. HꢀNMR (400
MHz, CDCl ): δ (ppm) 7.68~7.63 (m, 4H), 7.51~7.40 (m, 6H), 6.70 (ddt, J = 6.4 Hz, J = 16.8 Hz, J = 19.6 Hz,
1H), 6.22 (dd, J = 16.8 Hz, J = 24.0 Hz, 1H), 3.61 (t, J = 6.4 Hz, 2H), 2.33~2.30 (m, 2H), 1.99 (b, 1H), 1.61~1.50
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3
1
2
3
1
2
13
(m, 4H). CꢀNMR (100 MHz, CDCl
9.5 Hz), 128.5 (d, J = 12.4 Hz), 121.9 (d, J = 102.9 Hz), 62.4, 34.3 (d, J = 16.2 Hz), 32.2, 24.2. PꢀNMR (162
MHz, CDCl ): δ (ppm) 24.2.
Z)-(3,3-dimethylbut-1-en-1-yl)diphenylphosphine oxide [3e (Z)] . White solid; mp 116ꢀ117 C. HꢀNMR
400 MHz, CDCl ): δ (ppm) 7.70~7.64 (m, 4H), 7.41~7.34 (m, 6H), 6.62 (dd, J = 14.8 Hz, J = 43.6 Hz, 1H), 5.90
dd, J = 14.8 Hz, J = 22.8 Hz, 1H), 1.14 (s, 9H). CꢀNMR (100 MHz, CDCl ): δ (ppm) 164.6, 135.7 (d, J = 103.9
3
): δ (ppm) 152.4, 133.1 (d, J = 103.8 Hz), 131.7 (d, J = 2.9 Hz), 131.3 (d, J =
31
3
15
o
1
(
(
(
3
1
2
13
1
2
3
Hz), 131.3 (d, J = 2.0 Hz), 130.9 (d, J = 9.6 Hz), 128.5 (d, J = 11.4 Hz), 119.3 (d, J = 99.2 Hz), 35.5 (d, J = 4.8 Hz),
31
3
0.31. PꢀNMR (162 MHz, CDCl ): δ (ppm) 20.2.
3
13
o
1
(E)-(3,3-dimethylbut-1-en-1-yl)diphenylphosphine oxide [3e (E)]. White solid; mp 160ꢀ161 C. HꢀNMR
(400 MHz, CDCl ): δ (ppm) 7.69~7.63 (m, 4H), 7.52~7.41 (m, 6H), 6.75 (dd, J = 17.2 Hz, J = 20.4 Hz, 1H), 6.09
3
1
2
13
(
dd, J
1
2 3
= 17.2 Hz, J = 24.0 Hz, 1H), 1.09 (s, 9H). CꢀNMR (100 MHz, CDCl ): δ (ppm) 162.3, 133.4 (d, J = 103.9
Hz), 131.7 (d, J = 2.9 Hz), 131.3 (d, J = 9.6 Hz), 128.5 (d, J = 11.5 Hz), 116.5 (d, J = 102.9 Hz), 35.3 (d, J = 15.3
31
Hz), 28.7. PꢀNMR (162 MHz, CDCl
3
): δ (ppm) 24.8.
16
o
1
(
Z)-diphenyl(2-(trimethylsilyl)vinyl)phosphine oxide [3h (Z)]. White solid; mp 94ꢀ96 C. HꢀNMR (400
MHz, CDCl ): δ (ppm) 7.71~7.66 (m, 4H), 7.50~7.40 (m, 6H), 7.08 (dd, J = 17.2 Hz, J = 29.6 Hz, 1H), 6.98 (dd,
J = 17.2 Hz, J = 19.2 Hz, 1H), 0.24 (s, 9H). CꢀNMR (100 MHz, CDCl ): δ (ppm) 156.5 (d, J = 7.6 Hz), 138.4 (d,
3
1
2
1
3
1
2
3
J = 100.1 Hz), 134.0 (d, J = 101.0 Hz), 131.2 (d, J = 2.9 Hz), 130.8 (d, J = 9.6 Hz), 128.2 (d, J = 11.4 Hz), 0.08.
31
PꢀNMR (162 MHz, CDCl ): δ (ppm) 20.9.
3
13
o
1
(E)-diphenyl(2-(trimethylsilyl)vinyl)phosphine oxide [3h (E)]. White solid; mp 117ꢀ119 C. HꢀNMR (400
MHz, CDCl ): δ (ppm) 7.70~7.64 (m, 4H), 7.54~7.42 (m, 6H), 7.26 (dd, J = 20.4 Hz, J = 26.0 Hz, 1H), 6.84 (dd,
3
1
2
13
J
1
2 3
= 20.4 Hz, J = 31.6 Hz, 1H), 0.14 (s, 9H). CꢀNMR (100 MHz, CDCl ): δ (ppm) 155.2 (d, J = 5.7 Hz), 137.0 (d,
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J = 89.6 Hz), 132.7 (d, J = 102.0 Hz), 131.8 (d, J = 2.9 Hz), 131.4 (d, J = 10.4 Hz), 128.6 (d, J = 12.4 Hz), ꢀ1.8.
3
1
PꢀNMR: δ (ppm) 23.5.
Z)-diphenyl(2-(triisopropylsilyl)vinyl)phosphine oxide [3i (Z)]. White viscous tar. HꢀNMR (400 MHz,
CDCl ): δ (ppm) 7.71~7.66 (m, 4H), 7.49~7.39 (m, 6H), 7.18 (dd, J = 18.0 Hz, J = 34.4 Hz, 1H), 6.97 (dd, J
18.0 Hz, J = 50.0 Hz, 1H), 1.61~1.49 (m, 3H), 1.04 (d, J = 7.2 Hz, 18H). CꢀNMR (100 MHz, CDCl ): δ (ppm)
1
(
3
1
2
1
=
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
3
2
3
151.7 (d, J = 6.6 Hz), 140.0 (d, J = 101.0 Hz), 134.4 (d, J = 102.0 Hz), 131.4 (d, J = 2.9 Hz), 131.1 (d, J = 9.5 Hz),
3
1
128.5 (d, J = 12.4 Hz), 19.3, 12.8. PꢀNMR (162 MHz, CDCl ): δ (ppm) 19.9. GCꢀMS (EI, 70 eV) m/z = 342
3
+
+
(
[M+H] ꢀ CH(CH
)
3 2
, 27), 341 (M ꢀ CH(CH
3
)
2
, 100). Anal. Calcd for C23
H
33OPSi: C, 71.83; H, 8.65. Found: C,
71.67; H, 8.56.
16
1
(
E)-diphenyl(2-(triisopropylsilyl)vinyl)phosphine oxide [3i (E)]. White viscous tar. HꢀNMR (400 MHz,
CDCl ): δ (ppm) 7.69 ~7.64 (m, 4H), 7.53~7.42 (m, 6H), 7.16 (dd, J = 20.8Hz, J = 30.8 Hz, 1H), 6.92 (dd, J =
3
1
2
1
1
3
2
0.8 Hz, J
2
= 31.6 Hz, 1H), 1.20~1.10 (m, 3H), 1.04 (d, J = 6.8 Hz, 18H). CꢀNMR (100 MHz, CDCl
3
): δ (ppm)
150.6 (d, J = 5.7 Hz), 139.5 (d, J = 89.6 Hz), 132.8 (d, J = 102.0 Hz), 131.7 (d, J = 2.9 Hz), 131.4 (d, J = 9.5 Hz),
3
1
128.6 (d, J = 12.4 Hz), 18.6, 10.8. PꢀNMR (162 MHz, CDCl
3
): δ (ppm) 23.5.
1
(Z)-(3-hydroxyprop-1-en-1-yl)diphenylphosphine oxide [3j (Z)]. Colorless oil. HꢀNMR (400 MHz, CDCl ): δ
3
(ppm) 7.69~7.63 (m, 4H), 7.50~7.39 (m, 6H), 6.88 (ddt, J
1 2 3 1
= 4.4 Hz, J = 13.6 Hz, J = 40.0 Hz, 1H), 6.13 (ddt, J
13
=
1.6 Hz, J = 13.6 Hz, J = 24.8 Hz, 1H), 5.61 (b, 1H), 4.42 (b, 2H). CꢀNMR (100 MHz, CDCl ): δ (ppm) 153.4,
2
3
3
132.7 (d, J = 106.7 Hz), 132.1 (d, J = 1.9 Hz), 131.1 (d, J = 9.6 Hz, 128.7 (d, J = 12.4 Hz), 121.3 (d, J = 97.2 Hz),
31
+
6
1.2 (d, J = 8.6 Hz). PꢀNMR (162 MHz, CDCl ): δ (ppm) 26.8. GCꢀMS (EI, 70 eV) m/z = 259 ([M+H] , 3), 258
3
+
(
M , 16). Anal. Calcd for C15
H
15
2
O P: C, 69.76; H, 5.85. Found: C, 69.46; H, 5.78.
1
7
o
1
(
E)-(3-hydroxyprop-1-en-1-yl)diphenylphosphine oxide [3j (E)]. White solid, mp: 119ꢀ123 C. HꢀNMR
(
400 MHz, CDCl ): δ (ppm) 7.67~7.62 (m, 4H), 7.50~7.38 (m, 6H), 6.76~6.54 (m, 2H), 4.29~4.27 (m, 2H), 3.56 (b,
3
13
1H). CꢀNMR (100 MHz, CDCl ): δ (ppm) 152.1, 132.5 (d, J = 105.8 Hz), 131.9 (d, J = 2.8 Hz), 131.3 (d, J = 9.6
3
3
1
Hz), 128.6 (d, J = 12.4 Hz), 119.6 (d, J = 102.9 Hz), 62.8 (d, J = 17.1 Hz). PꢀNMR (162 MHz, CDCl
3
): δ (ppm)
26.1.
18
1
(
3-Hydroxypent-1-en-1-yl)diphenylphosphine oxide [3k (E + Z)]. White solid. HꢀNMR: δ (ppm) 7.68~7.59
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(
m, 4H, E + Z), 7.49~7.34 (m, 6H, E + Z), 6.82~6.67 (m, 1H, E + Z), 6.49 (ddd, J = 2.0 Hz, J = 16.8 Hz, J = 24.8
1
2
3
1 2 3
Hz, E), 6.08 (ddd, J = 1.6 Hz, J = 13.6 Hz, J = 25.2 Hz, Z), 5.39 (b, 1H, Z), 4.52~4.46 (m, 1H, Z), 4.22~4.20 (m,
13
1
H, E), 1.66~1.47 (m, 1H, E + Z), 0.89 (t, J = 7.2 Hz, E + Z). CꢀNMR (100 MHz, CDCl ): δ (ppm) 157.1 (Z),
3
1
54.0 (E), 133.1 (d, J = 105.8 Hz E + Z), 132.9 (d, J = 104.9 Hz, E + Z), 132.0 (d, J = 2.9 Hz, E + Z), 131.9 (d, J =
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
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6
7
8
9
0
1
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7
8
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0
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7
8
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0
2.9 Hz, E + Z), 131.3 (d, J = 4.8 Hz, E), 131.2 (d, J = 11.5 Hz, E + Z), 131.1 (d, J = 10.4 Hz, Z), 128.7 (d, J = 11.5
Hz, Z), 128.6 (d, J = 15.2 Hz, E), 121.2 (d, J = 97.2 Hz, E + Z), 73.2 (d, J = 14.3 Hz, E), 70.6 (d, J = 7.6 Hz, Z),
31
29.9 (Z), 29.6 (E), 9.9 (Z), 9.7 (E). PꢀNMR (162 MHz, CDCl ): δ (ppm) 26.0 (Z), 24.8 (E).
3
1
(
3-Hydroxy-3-methylpent-1-en-1-yl)diphenylphosphine oxide [3l (E + Z)]. White solid. HꢀNMR (400 MHz,
CDCl ): δ (ppm) 7.68~7.59 (m, 4H, E + Z), 7.48~7.37 (m, 6H, E + Z), 6.75 (dd, J = 16.8 Hz, J = 20.0 Hz, 1H, E),
3
1
2
6
1 2 1 2
.72 (dd, J = 14.4 Hz, J = 40.4 Hz, 1H, Z), 6.46 (dd, J = 16.8 Hz, J = 25.6 Hz, 1H, E), 6.32 (b, 1H, E + Z), 5.93
(dd, J = 14.4 Hz, J = 24.4 Hz, 1H, Z), 1.66~1.55 (m, 2H, E + Z), 1.32 (s, 3H, Z), 1.27 (s, 3H, E), 0.89 (t, J = 7.2
1
2
1
3
Hz, 3H, Z), 0.84 (t, J = 7.2 Hz, 3H, E). CꢀNMR (100 MHz, CDCl
3
): δ (ppm) 161.4 (Z), 157.3 (E), 133.2 (d, J =
1
05.8 Hz, E + Z), 133.1 (d, J = 106.8 Hz, E + Z), 131.9 (d, J = 1.9 Hz, Z), 131.8 (d, J = 1.9 Hz, E), 131.2 (d, J =
10.5 Hz, E + Z), 128.64 (d, J = 11.4 Hz, Z), 128.60 (d, J = 12.3 Hz, E + Z), 128.58 (d, J = 12.4 Hz, E), 118.5, (d, J
= 98.2 Hz, Z), 117.8 (d, J = 141.0 Hz, E), 73.7 (d, J = 6.7 Hz, E +Z), 35.7 (Z), 34.6 (E), 28.0 (Z), 27.5 (E), 8.5 (Z),
3
1
8
3
.1 (E). PꢀNMR (162 MHz, CDCl ): δ (ppm) 27.3 (Z), 24.5 (E). GCꢀMS (EI, 70 eV) 3l (Z) m/z = 283
+
+
+
+
([M+H] ꢀH O, 18), 282 (M ꢀH O, 72). 3l (E) m/z = 283 ([M+H] ꢀH O, 5), 282 (M ꢀH O, 11). Anal. Calcd for
2
2
2
2
C
H
18 21
O
2
P: C, 71.98; H, 7.05. Found: C, 71.98; H, 7.02.
3-Hydroxy-3-methylbut-1-en-1-yl)diphenylphosphine oxide [3m (E + Z)].
MHz, CDCl ): δ (ppm) 7.72~7.64 (m, 4H, E + Z), 7.53~7.39 (m, 6H, E +Z), 6.86 (dd, J
17, 19
1
(
White solid. HꢀNMR (400
3
1
= 16.8 Hz, J = 19.6 Hz,
2
1
H, E), 6.84 (dd, J = 14.0 Hz, J = 40.4 Hz, 1H, Z), 6.50 (dd, J = 16.8 Hz, J = 25.2 Hz, 1H, E), 6.49 (b, 1H, E +
1
2
1
2
13
Z), 5.92 (dd, J
1
2 3
= 14.0 Hz, J = 24.0 Hz, 1H, Z), 1.43 (s, 6H, Z), 1.35 (s, 6H, E). CꢀNMR (100 MHz, CDCl ): δ
(ppm) 162.0 (Z), 158.2 (E), 133.1 (d, J = 104.8 Hz, E), 132.9 (d, J = 106.7 Hz, Z), 131.9 (d, J = 6.1 Hz, Z), 131.7 (d,
J = 1.9 Hz, E), 131.24 (d, J = 9.5 Hz, E), 131.20 (d, J = 10.5 Hz, Z), 128.7 (d, J = 10.5 Hz, Z), 128.5 (d, J = 10.5 Hz,
E), 117.83 (d, J = 101.0 Hz, E), 117.75 (d, J = 97.3 Hz, Z), 71.9 (d, J = 15.3 Hz, E), 71.0 (d, J = 6.7 Hz, Z), 30.3 (Z),
31
2
9.4 (E). PꢀNMR (162 MHz, CDCl
3
): δ (ppm) 27.5 (Z), 24.5 (E).
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(
3-Hydroxy-3-phenylbut-1-en-1-yl)diphenylphosphine oxide [3n (E + Z)]. White solid. HꢀNMR (400 MHz,
CDCl ): δ (ppm) 7.75~6.98 (m, 16H, E + Z), 6.61 (dd, J = 17.2 Hz, J = 24.8 Hz, 1H, E), 6.00 (dd, J = 14.0 Hz, J
23.6 Hz, 1H, Z), 1.74 (s, 3H, Z), 1.69 (s, 3H, E). CꢀNMR (100 MHz, CDCl ): δ (ppm) 161.2 (Z), 156.6 (E),
3
1
2
1
2
13
=
3
1
46.9 (Z), 144.9 (E), 132.7 (d, J = 106.7 Hz, E + Z), 132.5 (d, J = 105.8 Hz, E + Z), 132.0 (d, J = 2.9 Hz, E + Z),
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
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6
7
8
9
0
1
2
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8
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0
131.9 (d, J = 2.8 Hz, E + Z), 131.3 (d, J = 10.5 Hz, E + Z), 131.23 (d, J = 9.5 Hz, E + Z), 131.15 (d, J = 10.5 Hz, E
+ Z), 128.7 (E + Z), 128.6 (d, J = 12.4 Hz, E + Z), 128.5 (d, J = 12.4 Hz, E + Z), 128.2 (E + Z), 126.8 (E + Z), 125.2
(E + Z), 118.6 (d, J = 96.3 Hz, E), 118.2 (d, J = 97.2 Hz, Z), 75.2 (d, J = 13.4 Hz, E), 74.7 (d, J = 6.7 Hz, Z), 31.2
31
(
(
Z), 29.3 (E). PꢀNMR (162 MHz, CDCl
3
): δ (ppm) 27.2 (Z), 24.5 (E). GCꢀMS (EI, 70 eV) 3n (Z) m/z = 331
+
+
+
[M+H] ꢀH O, 18), 330 (M ꢀH O, 72). 3n (E) m/z = 348 (M , 3). Anal. Calcd for C H O P: C, 75.85; H, 6.08.
2
2
22 21
2
Found: C, 75.62; H, 6.00.
2-(1-Hydroxycyclopentyl)vinyl)diphenylphosphine oxide [3o (E + Z)]. White solid. HꢀNMR (400 MHz,
CDCl ): δ (ppm) 7.67~7.59 (m, 4H, E + Z), 7.46~7.35 (m, 6H, E + Z), 6.82 (dd, J = 14.0 Hz, J = 40.4 Hz, 1H, Z),
.81 (dd, J = 16.8 Hz, J = 19.6 Hz, 1H, E), 6.52 (dd, J = 16.8 Hz, J = 25.6 Hz, 1H, E), 6.11 (b, 1H, Z), 5.93 (dd,
1
9
1
(
3
1
2
6
1
2
1
2
1
3
J
1
= 14.0 Hz, J
2 3
= 24.8 Hz, 1H, Z), 1.93~1.63 (m, 8H, E + Z). CꢀNMR (100 MHz, CDCl ): δ (ppm) 160.9 (Z),
157.6 (E), 133.2 (d, J = 104.9 Hz, E), 133.1 (d, J = 106.8 Hz, Z), 131.8 (d, J = 1.9 Hz, Z), 131.7 (d, J = 2.8 Hz, E),
1
31.23 (d, J = 9.5 Hz, E), 131.18 (d, J = 9.5 Hz, Z), 128.6 (d, J = 12.4 Hz, Z), 128.5 (d, J = 9.5 Hz, E), 118.4 (d, J =
9
8.1 Hz, Z), 117.9 (d, J = 102.0 Hz, E), 82.7 (d, J = 15.2 Hz, E), 81.5 (d, J = 6.7 Hz, Z), 41.4 (Z), 40.6 (E), 24.1 (E
31
+
Z). PꢀNMR (162 MHz, CDCl
3
): δ (ppm) 27.6 (Z), 24.6 (E).
1
(
Z)-tert-butyl(oct-1-en-1-yl)(phenyl)phosphine oxide [3q (Z)]. Colorless oil. HꢀNMR (400 MHz, CDCl ): δ
3
(
1 2 3 1
ppm) 7.70~7.65 (m, 2H), 7.45~7.35 (m, 3H), 6.62 (ddt, J = 7.6 Hz, J = 12.8 Hz, J = 37.2 Hz, 1H), 6.05 (dd, J =
13
1
2.8 Hz, J = 26.0 Hz, 1H), 2.50~2.35 (m, 2H), 1.31~1.04 (m, 17H), 0.75 (t, J = 6.8 Hz, 3H). CꢀNMR (100 MHz,
2
CDCl
3
): δ (ppm) 155.9, 132.2 (d, J = 91.5 Hz), 131.9 (d, J = 7.6 Hz), 131.2 (d, J = 2.9 Hz), 128.0 (d, J = 10.5 Hz),
31
116.9 (d, J = 91.5 Hz), 32.8 (d, J = 72.4 Hz), 31.6, 30.8 (d, J = 6.6 Hz), 28.9, 24.1, 22.5, 14.1, 1.1. PꢀNMR (162
+
+
MHz, CDCl
C, 73.94; H, 10.00. Found: C, 73.99; H, 9.87.
3
E)-tert-butyl(oct-1-en-1-yl)(phenyl)phosphine oxide [3q (E)]. Colorless oil. HꢀNMR (400 MHz, CDCl ): δ
3
): δ (ppm) 38.1. GCꢀMS (EI, 70 eV) m/z = 293 ([M+H] , 6), 292 (M , 30). Anal. Calcd for C18H29OP:
20
1
(
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(
ppm) 7.69~7.65 (m, 2H), 7.45~7.35 (m, 3H), 6.82 (ddt, J = 6.8 Hz, J = J = 17.6 Hz, 1H), 6.19 (dd, J = 17.6 Hz,
1
2
3
1
J
2
= 28.0 Hz, 1H), 2.26~2.21 (m, 2H), 1.45~1.37 (m, 2H), 1.29~1.19 (m, 6H), 1.04 (d, J = 14.8 Hz, 9H), 0.81 (t, J =
1
3
6
.8 Hz, 3H). CꢀNMR (100 MHz, CDCl ): δ (ppm) 153.9, 131.9 (d, J = 70.5 Hz), 131.8 (d, J = 8.6 Hz), 131.3 (d, J
3
=
1.9 Hz), 128.1 (d, J = 10.5 Hz), 117.3 (d, J = 92.4 Hz), 34.8 (d, J = 15.3 Hz), 32.6 (d, J = 72.4 Hz), 31.6, 28.9,
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
3
1
24.2, 22.6, 14.1, 1.1. PꢀNMR (162 MHz, CDCl ): δ (ppm) 38.2.
3
1
3
Oct-1-en-1-ylbis(4-phenylbutyl)phosphine oxide [3r (E + Z)]. Colorless oil. HꢀNMR (400 MHz, CDCl ): δ
(ppm) 7.21~7.18 (m, 4H, E + Z), 7.12~7.07 (m, 6H, E + Z), 6.61 (ddt, J = 6.8 Hz, J = J =17.6 Hz, 1H, E), 6.41
1
2
3
(ddt, J
1
= 7.6 Hz, J
2
= 13.2 Hz, J
3
= 38.0 Hz, 1H, Z), 5.53 (dd, J
1
2 1
= 17.6 Hz, J = 27.6 Hz, 1H, E), 5.31 (dd, J =
1
3.2 Hz, J = 26.8 Hz, 1H, Z), 2.57~2.53 (m, 6H, E), 2.17~2.11 (m, 6H, Z), 1.69~1.53 (m, 12H, E + Z), 1.37~1.21
2
13
(
(
m, 8H, E + Z), 0.83 (t, J = 6.8 Hz, 3H, E), 0.82 (t, J = 6.8 Hz, 3H, Z). CꢀNMR (100 MHz, CDCl
3
): δ (ppm) 154.0
Z), 152.2 (E), 141.93 (Z), 141.90 (E), 128.3 (E + Z), 125.8 (E + Z), 121.0 (d, J = 91.5 Hz, E), 120.2 (d, J = 89.6 Hz,
Z), 35.53 (Z), 35.46 (E), 34.4 (d, J = 15.2 Hz, E), 32.9 (d, J = 14.3 Hz, Z), 32.8 (d, J = 14.3 Hz, E), 30.9 (d, J =
72.5 Hz, Z), 30.71 (d, J = 179.2 Hz, E), 30.68 (Z), 30.2 (d, J = 6.6 Hz, Z), 29.2 (d, J = 36.2 Hz, Z), 29.0 (d, J =
34.3 Hz, E), 28.0 (E), 22.6 (E + Z), 21.5 (d, J = 3.8 Hz, Z), 21.3 (d, J = 2.8 Hz, E), 14.1 (E + Z), 1.0 (E + Z).
1
31
+
PꢀNMR (162 MHz, CDCl ): δ (ppm) 39.0 (Z), 37.8 (E). GCꢀMS (EI, 70 eV) 3r (Z) m/z = 425 ([M+H] , 9) 424
3
+
+
+
(M , 30). 3r (E) m/z = 425 ([M+H] , 8), 424 (M , 27). Anal. Calcd for C28
H41OP: C, 79.20; H, 9.73. Found: C,
7
8.96; H, 9.60.
1
(
Z)-dicyclohexyl(oct-1-en-1-yl)phosphine oxide [3s (Z)]. White viscous tar. HꢀNMR: δ (ppm) 6.55 (ddt, J
1
=
7
.2 Hz, J = 12.8 Hz, J = 36.8 Hz, 1H), 5.25 (dd, J = 12.8 Hz, J = 26.0 Hz, 1H), 2.65~2.60 (m, 2H), 1.96~1.93
2
3
1
2
1
3
(
m, 2H), 1.80~1.64 (m, 10H), 1.39~1.21 (m, 18H), 0.84 (t, J = 6.8 Hz, 3H). CꢀNMR (100 MHz, CDCl
3
): δ (ppm)
1
2
55.4, 117.1 (d, J = 84.8 Hz), 36.1 (d, J = 68.6 Hz), 31.7, 30.0 (d, J = 5.7 Hz), 29.5, 29.0, 26.6 (d, J = 12.4 Hz),
3
1
3
6.4 (d, J = 12.4 Hz), 26.0, 25.8 (d, J = 1.9 Hz), 24.7 (d, J = 2.8 Hz), 22.6, 14.1. PꢀNMR (162 MHz, CDCl ): δ
+
+
(ppm) 45.6. GCꢀMS (EI, 70 eV) m/z = 325 ([M+H] , 5), 324 (M , 21). Anal. Calcd for C H OP: C, 74.03; H,
20
37
11.49. Found: C, 73.96; H, 11.34.
E)-dicyclohexyl(oct-1-en-1-yl)phosphine oxide [3s (E)]. White solid; mp 60ꢀ62 C. HꢀNMR (400 MHz,
CDCl ): δ (ppm) 6.66 (ddt, J = 6.4 Hz, J = J = 16.8 Hz, 1H), 5.52 (dd, J = 16.8 Hz, J = 27.2 Hz, 1H), 2.25~2.20
o
1
(
3
1
2
3
1
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(
m, 2H), 1.95~1.92 (m, 2H), 1.80~1.64 (m, 10H), 1.45~1.19 (m 18H), 0.86 (t, J = 6.8 Hz, 3H). CꢀNMR (100
MHz, CDCl ): δ (ppm) 153.3, 117.9 (d, J = 86.7 Hz), 35.3 (d, J = 68.6 Hz), 34.6 (d, J = 15.2 Hz), 31.6, 28.8, 28.1,
6.6 (d, J = 12.4 Hz), 26.4 (d, J = 12.4 Hz), 26.0, 25.7 (d, J = 2.9 Hz), 24.7 (d, J = 3.8 Hz), 22.6, 14.1. PꢀNMR
3
3
1
2
+
+
(162 MHz, CDCl
3
): δ (ppm) 43.1. GCꢀMS (EI, 70 eV) m/z = 325 ([M+H] , 3), 324 (M , 14). Anal. Calcd for
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
C H OP: C, 74.03; H, 11.49. Found: C, 73.97; H, 11.43.
2
0
37
2
1
1
Ethyl -oct-1-en-1-yl(phenyl)phosphinate [3t (E + Z)]. Colorless oil. HꢀNMR (400 MHz, CDCl
3
): δ (ppm)
7.80~7.73 (m, 2H, E + Z), 7.52~7.40 (m, 3H, E + Z), 6.74 (ddt, J = 6.4 Hz, J = 16.8 Hz, J = 20.0 Hz, 1H, E),
1
2
3
6
3
1 2 3
.44 (ddt, J = 7.6 Hz, J = 12.8 Hz, J = 46.0 Hz, 1H, Z), 5.91~5.76 (m, 1H, E + Z), 4.10~4.00 (m, 1H, E + Z),
.98~3.84 (m, 1H, E + Z), 2.51~2.38 (m, 2H, Z), 2.22~2.16 (m, 2H, E), 1.32~1.15 (m, 11H, E + Z), 0.84 (t, J = 6.4
13
Hz, 3H, E), 0.82 (t, J = 6.4 Hz, 3H, Z). CꢀNMR (100 MHz, CDCl
3
): δ (ppm) 153.8 (d, J = 3.8 Hz, Z), 153.1 (d, J
=
3.8 Hz, E), 132.9 (d, J = 131.5 Hz, Z), 132.0 (d, J = 2.8 Hz, E), 131.9 (d, J = 2.9 Hz, Z), 131.7 (d, J = 134.3 Hz,
E), 131.4 (d, J = 10.5 Hz, E), 131.3 (d, J = 10.5 Hz, Z), 128.5 (d, J = 12.4 Hz, E), 128.4 (d, J = 13.3 Hz, Z), 120.6
d, J = 136.3 Hz, E), 120.5 (d, J = 135.1 Hz, Z), 60.6 (d, J = 5.7 Hz, E), 60.3 (d, J = 5.7 Hz, Z), 34.3 (d, J = 18.1 Hz,
E), 31.62 (Z), 31.59 (E), 30.7 (d, J = 8.6 Hz, Z), 28.84 (E +Z), 28.81 (Z), 27.8 (E), 22.6 (E + Z), 16.5 (d, J = 6.6 Hz,
(
31
E + Z), 14.1 (E + Z). PꢀNMR (162 MHz, CDCl ): δ (ppm) 31.4 (E), 30.6 (Z).
3
4
d
o
1
Octane-1,2-diylbis(diphenylphosphine oxide) (4a). White solid; mp 147ꢀ148 C. HꢀNMR (400 MHz,
CDCl ): δ (ppm) 7.79~7.68 (m, 6H), 7.49~7.32 (m, 14H), 3.02~2.95 (m, 1H), 2.67~2.47 (m, 2H), 1.79~1.63 (m,
3
13
1
H), 1.49~1.37 (m, 1H), 1.29~1.17 (m, 1H), 1.06~0.97 (m, 2H), 0.94~0.79 (m, 3H), 0.78~0.69 (m, 5H). CꢀNMR
(
100 MHz, CDCl ): δ (ppm) 133.31 (d, J = 97.3 Hz), 133.25 (d, J = 99.1 Hz), 132.1 (d, J = 91.5 Hz), 132.0 (d, J =
3
9
4.3 Hz) 131.8 (d, J = 1.9 Hz), 131.7 (d, J = 2.9 Hz), 131.1 (d, J = 7.6 Hz), 130.9 (d, J = 8.6 Hz), 130.7 (d, J = 8.6
Hz), 130.6 (d, J = 9.6 Hz), 128.8 (d, J = 11.5 Hz), 128.6 (d, J = 11.4 Hz), 128.5 (d, J = 10.5 Hz), 31.3 (dd, J = 2.9
1
31
Hz, J
2
= 68.6 Hz), 31.1, 29.2, 28.3, 27.5 (d, J = 68.6 Hz), 27.0 (d, J = 3.8 Hz), 22.4, 14.0. PꢀNMR (162 MHz,
CDCl ): δ (ppm) 37.8 (d, J = 44.9 Hz), 30.8 (d, J = 44.9 Hz).
3
2
2
Octyldiphenylphosphine oxide (5). A mixture of diphenylphosphine oxide (24.3 mg, 0.12 mmol), 1ꢀoctyne
(
11.0 mg, 0.1 mmol) and 1ꢀoctene (11.2 mg, 0.1 mmol) in iꢀPrOH (0.3 mL) was sealed in a Pyrexꢀtube under
nitrogen and was irradiated using a highꢀpressure Hg lamp (Ushio, SXꢀU1501HQ) for 4 h. The reaction mixture
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was concentrated under vacuum. The crude product was purified by HPLC to obtain the target compound (6.0 mg,
o
1
1
9% yield). White solid; mp 57ꢀ58 C. HꢀNMR (400 MHz, CDCl
3
): δ (ppm) 7.74~7.68 (m, 4H), 7.51~7.41 (m,
6H), 2.27~2.20 (m, 2H), 1.65~1.55 (m, 2H), 1.40~1.33 (m, 2H), 1.26~1.20 (m, 8H), 0.83 (t, J = 6.8 Hz, 3H).
1
3
CꢀNMR (100 MHz, CDCl
J = 11.4 Hz), 31.8, 31.0 (d, J = 14.3 Hz), 29.8 (d, J = 71.5 Hz), 22.6, 21.5 (d, J = 3.8 Hz), 14.1. PꢀNMR (162
MHz, CDCl ): δ (ppm) 33.3.
3
): δ (ppm) 133.2 (d, J = 97.2 Hz), 131.6 (d, J = 2.9 Hz), 130.8 (d, J = 8.5 Hz), 128.6 (d,
0
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AUTHOR INFORMATION
Corresponding Author
*Eꢀmail: ogawa@chem.osakafuꢀu.ac.jp (A.O.);
*E-mail: libiao-han@aist.go.jp (L.-B.H.)
Notes
The authors declare no competing financial interest.
SUPPORTING INFORMATION
1
13
31
H, C and P NMR spectroscopies for products. This material is available free of charge via the internet at
http://pubs.acs.org.
ACKNOWLEDGMENT
H.T. is a recipient of a student scholarship from CGGSOS program sponsored by China Scholarship Council
(
CSC) (20153022).
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(
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(
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2) Selected reviews on transitionꢀmetalꢀcatalyzed addition of P(O)H compounds to alkynes: (a) Alonso, F.;
(
Beletskaya, I. P.; Yus, M. TransitionꢀMetalꢀCatalyzed Addition of HeteroatomꢀHydrogen Bonds to Alkynes. Chem.
Rev. 2004, 104, 3079ꢀ3160. (b) Xu, Q.; Han, L.ꢀB. Metalꢀcatalyzed Additions of HꢀP(O) Bonds to CarbonꢀCarbon
Unsaturated Bonds. J. Organomet. Chem. 2011, 696, 130ꢀ140. (c) Demmer, C. S.; KrogsgaardꢀLarsen, N.; Bunch L.
Review on Modern Advances of Chemical Methods for the Introduction of a Phosphonic Acid Group. Chem. Rev.
2011, 111, 7981ꢀ8006.
(3) For coordination of P(O)ꢀH compounds with metals, see: (a) Shaikh, T. M.; Weng, C.ꢀM.; Hong, F.ꢀE.
Secondary Phosphine Oxides: Versatile Ligands in Transition Metalꢀcatalyzed Crossꢀcoupling Reactions. Coord.
Chem. Rev. 2012, 256, 771ꢀ803. (b) Li, G. Y. The First Phosphine Oxide Ligand Precursors for Transition Metal
Catalyzed CrossꢀCoupling Reactions: CꢀC, CꢀN and CꢀS Bond Formation on Unactivated Aryl Chlorides. Angew.
Chem. Int. Ed. 2001, 40, 1513ꢀ1516. (c) Wang, X.ꢀB.; Goto, M.; Han, L.ꢀB. Efficient Asymmetric Hydrogenation
of αꢀAcetamidocinnamates through a Simple, Readily Available Monodentate Chiral HꢀPhosphonate. Chem. Eur. J.
2014, 20, 3631ꢀ3635. (d) Janesko, B. G.; Fisher, H. C.; Bridle, M. J.; Montchamp, J.ꢀL. P(=O)H to PꢀOH
Tautomerism: A Theoretical and Experimental Study. J. Org. Chem. 2015, 80, 10025ꢀ10032. (e) Duncan, J. A. S.;
Hedden, D.; Roundhill, D. M.; Stephenson, T. A.; Walkinshaw, M. D. Synthesis of Novel Iridium and Rhodium
Complexes Containing Diphenylphosphinito and Dimethylphosphito Ligands. Angew. Chem., Int. Ed. 1982, 21,
452ꢀ453.
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(
4) (a) Staderini, S.; Dondoni, A.; Marra, A. Metalꢀfree Synthesis of Eꢀvinylphosphonates via Photoinduced
Alkyne Hydrophosphonylation and Thiol Promoted Isomerization Sequence. Tetrahedron Lett. 2015, 56, 374ꢀ377.
b) Geant, P.ꢀY.; Mohamed, B. S.; Perigaud, C.; Peyrottes, S.; Uttaro, J.ꢀP.; Mathe, C. Probing the Reactivity of
(
Hꢀphosphonate Derivatives for the Hydrophosphonylation of Various Alkenes and Alkynes under Freeꢀradical
Conditions. New J. Chem. 2016, 40, 5318ꢀ5324. (c) Hirai, T.; Han, L.ꢀB. Airꢀinduced antiꢀMarkovnikov Addition
of Secondary Phosphine Oxides and HꢀPhosphinates to Alkenes. Org. Lett. 2007, 9, 53ꢀ55. (d) Guo, H.; Yoshimura,
A.; Chen, T.; Saga, Y.; Han, L.ꢀB. Airꢀinduced Double Addition of P(O)ꢀH Bonds to Alkynes: A Clean and Practical
Method for the Preparation of 1,2ꢀbisphosphorylethanes. Green. Chem. 2017, 19, 1502ꢀ1506. (e) Li, M.ꢀS.; Zhang,
Q.; Hu, D.ꢀY.; Zhong, W.ꢀW.; Cheng, M.; Ji, J.ꢀX.; Wei, W. Catalystꢀfree Direct Difunctionalization of Alkenes with
Hꢀphosphine Oxide and Dioxygen: A Facile and Green Approach to βꢀHydroxyphosphine Oxides. Tetrahedron Lett.
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016, 57, 2642ꢀ2646. (f) Peng, P.; Lu, Q.ꢀQ.; Peng, L.; Liu, C.; Wang, G.ꢀY.; Lei, A.ꢀW. Dioxygenꢀinduced
Oxidative Activation of a PꢀH Bond: Radical Oxyphosphorylation of Alkenes and Alkynes toward βꢀOxy
Phosphonates. Chem. Commun. 2016, 52, 12338ꢀ12341. (g) Nifant`ev, E. E.; Solovetskaya, L.A.; Magdeeva, R. K.
Hydrophosphorylation of Alkynes with Phosphinous Acids. J. Gen. Chem. USSR (Engl. Transl.) 1985, 55,
2263ꢀ2269. For photoꢀinduced addition of Ph P(O)H to terminal alkenes, see (h) Kawaguchi, S.ꢀI.; Nomoto, A.;
2
Sonoda, M.; Ogawa, A. Photoinduced Hydrophosphinylation of Alkenes with Diphenylphosphine Oxide.
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(
5) Chen, T.; Zhao, C.; Han, L.ꢀB. Hydrophosphorylation of Alkynes Catalyzed by Palladium: Generality and
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6) A xenon lamp gave similar results, because a Pyrex tube was used, hv > 300 nm was the actual light source
(
for the reaction. In a Quartz tube (hv > 200 nm), the reaction also took place, despite a Z/E ratio of 38/62 was
obtained under the conditions of run 1. A separate reaction confirmed that while Zꢀ3a does not isomerize to Eꢀ3a in
a Pyrex tube, this isomerization of Zꢀ3a to Eꢀ3a took place rapidly in a Quartz tube.
(7) The reaction should not be conducted at a more elevated temperature because the formation of 4a increased
(
see ref 4d).
(8) Phenylacetylene was slowly consumed (6% consumed after 4 h, and 12% consumed after 16 h), and the
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oligomerization products of phenylacetylene could be detected. However, Ph P(O)H remained unchanged even
2
after 16 h.
(
9) For a discussion, see Han, L.ꢀB.; Ishihara, K.ꢀI.; Kambe, N.; Ogawa, A.; Ryu, I.; Sonoda, N. Carbotelluration
of Alkynes. J. Am. Chem. Soc. 1992, 114, 7591ꢀ7592.
(10) Halfꢀlife (10 h) temperatures of these radical initiators: AIBN, 65 C; Vꢀ601, 66 C; Vꢀ70, 30 C.
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(11) Only trace amount of the addition products (<5% estimated by P NMR) could be detected from the
o
reaction of phenylacetylene (0.2 mmol) with Ph P(O)H (0.1 mmol) in THF (0.5 mL) heated at 70 C in the
2
presence of 10mol% AIBN. While some oligomerization of phenylacetylene was observed, most of Ph
2
P(O)H
remained unchanged.
(
12) Niu, M.; Fu, H.; Jiang, Y.; Zhao, Y. Copperꢀcatalyzed Addition of Hꢀphosphine Oxides to Alkynes Forming
Alkenylphosphine Oxides. Chem. Commun. 2007, 272ꢀ274.
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(
Acetylenes with Diphenylphosphine Oxide Catalyzed by Immobilization of Rhodium in MCMꢀ41. J. Organomet.
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(17) Trostyanskaya, I. G.; Beletskaya, I. P. Copper (II)ꢀcatalyzed Regioꢀ and Stereoselective Addition of HP(O)R
2
to Alkynes. Tetrahedron 2014, 70, 2556ꢀ2562.
(18) Bartels, B.; Clayden, J.; Martín, C. G.; Nelson, A.; Russell, M. G.; Warren, S. Diastereoselective
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Nucleophilic Additions to Vinyl Phosphine Oxides. J. Chem. Soc., Perkin Trans. 1, 1999, 1807ꢀ1822.
(19) Bogachenkov, A. V.; Dogadina, A. V.; Boyarskiy, V. P.; Vasilyev, A. V. Acidꢀpromoted Transformations of
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3, 1333ꢀ1338.
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(20) Chen. T.; Zhou, Y.; Guo, C.; Han, L.ꢀB. Selective Addition of P(O)–H Bonds to Alkynes Catalyzed by
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(
22) Wang, F.; Qu, M.; Chen, F.; Xu, Q.; Shi, M. Ph PI as a Reduction/Phosphination Reagent: Providing Easy
2
Access to Phosphine Oxides. Chem. Commun. 2012, 48, 8580ꢀ8582.
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