Preparation of chiral multifunctional thiourea-phosphanes and synthesis of chiral allylic phosphites and phosphane oxides through asymmetric allylic substitution reactions of morita-baylis-hillman carbonates

Article abstract of DOI:10.1002/ejoc.201101365

We developed a synthetic method to prepare chiral multifunctional thiourea-phosphane catalysts for the asymmetric allylic substitution reaction of Morita-Baylis-Hillman carbonates with diphenyl phosphite or diphenylphosphane oxide to give allylic phosphit

Full text of DOI:10.1002/ejoc.201101365

FULL PAPER
DOI: 10.1002/ejoc.201101365
Preparation of Chiral Multifunctional Thiourea–Phosphanes and Synthesis of
Chiral Allylic Phosphites and Phosphane Oxides through Asymmetric Allylic
Substitution Reactions of Morita–Baylis–Hillman Carbonates
Hong-Ping Deng[a] and Min Shi*[a]
Keywords: Organocatalysis / Asymmetric catalysis / Allylic compounds / Amines
We developed a synthetic method to prepare chiral multi-
functional thiourea–phosphane catalysts for the asymmetric
allylic substitution reaction of Morita–Baylis–Hillman carbon-
ates with diphenyl phosphite or diphenylphosphane oxide to
give allylic phosphites and allylic phosphane oxides in high
yields with excellent enantioselectivity.
oped a series of thiourea–phosphane catalysts synthesized
from chiral trans-2-amino-1-(diphenylphosphanyl)cyclohex-
ane that catalyzed imine–allenate [3+2] cycloaddition reac-
tions with high enantioselectivity.[5] Meanwhile, Wu and co-
workers used these chiral multifunctional thiourea–phos-
phanes as catalysts in a variety of inter- and intramolecular
asymmetric MBH reactions and intramolecular asymmetric
Rauhut–Currier reactions, giving the corresponding prod-
ucts in good yields with high enantiomeric excess (ee) val-
ues.[6] More recently, Lu synthesized chiral multifunctional
thiourea–phosphanes from α-amino acids and used them to
catalyze asymmetric [3+2] annulations of MBH carbonates
and isatylidene malononitriles to give the corresponding
spirocyclopenteneoxindoles in excellent yields with excellent
diastereo- and enantioselectivities.[7]
Very recently, we have been working on the synthesis of
chiral multifunctional thiourea–phosphane catalysts from
axially chiral binaphthyl scaffolds that are highly active and
enantioselective catalysts in both the asymmetric aza-MBH
reaction and asymmetric allylic substitution reactions of
MBH adducts.[8] These catalysts were synthesized by heat-
ing precatalyst I with the corresponding isothiocyanate in
tetrahydrofuran (THF) at 60 °C for 3–5 d. For example, TP-
I was prepared by heating compound I with phenyl isothio-
cyanate in THF at 60 °C for 153 h and was isolated in 70%
yield after purification [Scheme 1, Equation (1)]. Interest-
ingly, if the reaction was heated to reflux in THF, within
2 d isothiocyanate–phosphane compound II was obtained
in 54% yield along with TP-I in 20% yield [Scheme 1,
Equation (2)]. A mechanism for the formation of com-
pound II is proposed in the Supporting Information. The
structure of compound II was determined by X-ray diffrac-
tion studies (Figure 1).[9] Compound II is a very useful in-
termediate precatalyst in the preparation of chiral multi-
functional thiourea–phosphanes because readily available
amines can be used as starting reagents rather than isothio-
cyanates, which are much more difficult to prepare. There-
Introduction
Chiral multifunctional phosphane organocatalysts, which
contain Lewis basic and Brønsted acidic sites within one
molecule, have received considerable attention because they
are highly active catalysts for enantioselective Morita–
Baylis–Hillman (MBH) reactions, aza-Morita–Baylis–Hill-
man (aza-MBH) reactions, cycloaddition reactions of al-
lenoates with electron-deficient olefins, and other related re-
actions.[1] To date, the synthesis of chiral multifunctional
phosphane catalysts has focused on the following three
classes of compounds: hydroxy–phosphanes, amide–phos-
phanes and thiourea–phosphanes. For example, our group,
Sasai, and Liu have developed a series of chiral multifunc-
tional hydroxy–phosphane organocatalysts derived from an
axially chiral binaphthyl scaffold that could effectively cata-
lyze MBH and aza-MBH reactions.[2] Moreover, our group
and Lu and co-workers have synthesized a series of chiral
multifunctional amide–phosphanes that are very efficient
catalysts for asymmetric aza-MBH reactions and asymmet-
ric allylic substitution reactions of MBH acetates, affording
the corresponding products in good yields with high
enantioselectivities under mild conditions.[3] The groups of
Miller, Zhao, and Lu have also recently reported the synthe-
sis of chiral multifunctional amide–phosphanes from α-
amino acids. These compounds catalyzed asymmetric [3+2]
cycloadditions of allenoates and electron-deficient olefins,
giving the corresponding cyclopentene derivatives in excel-
lent yields with excellent diastereo- and enantioselectivit-
ies.[4] Furthermore, in 2008, Jacobson and co-workers devel-
[a] State Key Laboratory of Organometallic Chemistry,
Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences,
354 Fenglin Road, Shanghai 200032, China
Fax: +86-21-64166128
E-mail: mshi@mail.sioc.ac.cn
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201101365.
Eur. J. Org. Chem. 2012, 183–187
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
183

H.-P. Deng, M. Shi
FULL PAPER
fore, we synthesized a series of multifunctional thiourea–
phosphane catalysts TP1–TP10 by using various anilines,
benzylamines, (1S,2R)-(–)-cis-1-amino-2-indanol, and Betti
bases in 61–89% yield in dichloromethane (CH2Cl2) within
12 h at room temperature (Scheme 2).[10] A further advan-
tage of this method is that the synthesis is carried out at
room temperature.
Scheme 1. Synthesis of chiral multifunctional thiourea–phosphane
catalysts.
Scheme 2. Preparation of chiral multifunctional thiourea–phos-
phane catalysts TP1–TP10.
alkenes and alkynes by fluoride ion activation in an ionic
liquid medium.[16] In 2004, Krische[17] reported chiral phos-
phane-catalyzed asymmetric substitution reactions of MBH
acetates with phthalimide and its derivatives to give the cor-
responding products in good yields with moderate ee val-
ues. Herein, we report new chiral multifunctional thiourea–
phosphane catalysts for asymmetric allylic substitution re-
actions of MBH carbonates with diphenyl phosphite or di-
phenylphosphane oxide to efficiently synthesize allylic
phosphites and phosphane oxides in good yields and with
high ee values under mild conditions.
Figure 1. ORTEP representation of the molecular structure of com-
pound II.
Recently, chiral phosphorus compounds have attracted
much attention because of their application in metal-cata-
lyzed or organocatalyst-catalyzed asymmetric reactions as
well as the promising biological properties of chiral amino-
phosphonic acids and their derivatives.[1,11,12] Although nu-
merous methods for the enantioselective construction of C–
P bonds have been reported, few have been used in the
preparation of chiral allylic phosphites and phosphane ox-
ides.[13] In 2010, Wang reported the use of cinchona alka-
loids as catalysts to synthesize chiral allylic phosphane ox-
ides through asymmetric substitution of MBH carbonates
Results and Discussion
Initially, we examined multifunctional thiourea–phos-
with phosphane oxide under mild conditions in excellent phanes catalysts TP1–TP10 (Scheme 2) in the asymmetric
yields and with high enantioselectivities.[8b,8c,14b,14c,15] Later, allylic substitution reaction of MBH carbonate 1a with di-
Swamy demonstrated hydrophosphonylation of activated phenyl phosphite (2a). The results are summarized in
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Allylic Phosphites and Phosphane Oxides by Allylic Substitution Reactions
Table 1. We tested catalysts TP1–TP5 in reactions of 1a CH2Cl2 at room temperature and found that TP1, which
with 2a in the presence of 4 Å molecular sieves (MS) in was an excellent catalyst for the asymmetric aza-MBH reac-
tion,[8a] did not catalyze this reaction (Table 1, Entry 1).
However, TP2–TP5 were fairly effective catalysts in this re-
Table 1. Optimization of the reaction conditions for the asymmetric
action. TP5 performed best, affording product 3a in 96%
yield and 73%ee at room temperature (Table 1, Entries 2–
5). Next, we examined the effect of solvent and temperature
by using TP5 as the catalyst and found that CH2Cl2, 1,2-
dichloroethane (DCE), and PhCN were better solvents, giv-
ing 3a in excellent yield and 73, 72, and 76%ee, respectively,
at room temperature (Table 1, Entries 5, 9, and 11). The use
of THF, CH3CN, or CCl4 as solvent afforded 3a in lower
yields at room temperature (Table 1, Entries 7, 8, and 10).
The use of toluene or PhCH2CN as the solvent gave poorer
enantioselectivity (Table 1, Entries 6 and 12). Lowering the
reaction temperature to 0 °C produced 3a in 80% yield with
80%ee in PhCN (Table 1, Entry 13). Decreasing the reac-
tion temperature to –20 °C gave 3a in 85% yield with
83%ee in CH2Cl2 (Table 1, Entry 14), but further reduction
of the reaction temperature to –78 °C gave a lower yield
with lower enantioselectivity (Table 1, Entry 15). In CH2Cl2
at –20 °C, we tested catalysts TP6–TP10 and found that
TP10 was the most efficient, resulting in 3a in 57% yield
with 97%ee (Table 1, Entries 16–20). The optimum condi-
tions for the reaction were found to be a temperature of
0 °C, affording 3a in 82% yield and 90%ee (Table 1, En-
try 21).
Under these optimal conditions, we investigated the
scope of this reaction with various MBH carbonates 1b–m.
The results are summarized in Table 2. All of the reactions
proceeded smoothly, providing desired products 3a–m in
good yields (70–87%) with excellent enantioselectivity (94–
97%ee) regardless of whether they had electron-with-
drawing or electron-donating substituents on their aromatic
rings (Table 2, Entries 1–11). Introducing more than one
substituent on the aromatic ring gave the corresponding
product 3l in 72% yield with 95%ee (Table 2, Entry 12).
MBH carbonate 1m, derived from ethyl vinyl ketone, also
gave a good result, affording 3m in 75% yield with 96%ee
(Table 2, Entry 13).
allylic substitution reaction of MBH carbonate 1a with diphenyl
phosphite (2a).[a]
Entry
Catalyst
Solvent
T [°C]
Yield [%][b] ee [%][c]
1
2
3
4
5
6
7
8
TP1
TP2
TP3
TP4
TP5
TP5
TP5
TP5
TP5
TP5
TP5
TP5
TP5
TP5
TP5
TP6
TP7
TP8
TP9
TP10
TP10
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
toluene
CH3CN
THF
DCE
CCl4
PhCN
PhCH2CN
PhCN
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
0
–20
–78
–20
–20
–20
–20
–20
0
–
–
94
91
87
96
87
25
16
91
43
89
85
80
85
48
91
85
80
53
57
82
70 (–)
66 (–)
71 (–)
73 (–)
42 (–)
81 (–)
31 (–)
72 (–)
48 (–)
76 (–)
63 (–)
80 (–)
83 (–)
73 (–)
64 (–)
89 (–)
80 (–)
91 (–)
97 (–)
90 (–)
9
10
11
12
13
14
15
16
17[d]
18[d]
19[d]
20[d]
21
[a] All reactions were carried out with 1a (0.1 mmol) and 2a
(0.2 mmol) in the presence of catalyst and 4 Å MS (50 mg) in sol-
vent (1.0 mL). [b] Isolated yield. [c] Determined by chiral HPLC.
[d] Reactions were performed for 48 h.
Table 2. Substrate scope for the asymmetric allylic substitution re-
action of MBH carbonates 1 with diphenyl phosphite (2a).[a]
Table 3. Substrate scope for the asymmetric allylic substitution re-
action of MBH carbonates 1 with diphenylphosphane oxide (2b).[a]
Entry
R1
R2
Yield [%][b]
ee [%][c]
1
2
3
4
5
6
7
8
1a, 4-NO2
1b, 3-NO2
1c, 4-CF3
1d, 4-CN
1e, 4-Br
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Et
3a, 82
3b, 87
3c, 78
3d, 79
3e, 81
3f, 83
3g, 70
3h, 87
3i, 75
3j, 71
3k, 81
3l, 72
3m, 75
90 (+)
96 (+)
96 (+)
95 (+)
96 (+)
94 (+)
97 (+)
95 (+)
97 (+)
96 (+)
96 (+)
95 (+)
96 (+)
1f, 4-MeSO2
1g, 4-Cl
Entry
R1
R2
Yield [%][b]
ee [%][c]
1h, 3-Cl
9
1i, 2-Cl
1
2
3
4
5
1a, 4-NO2
1e, 4-Br
1g, 4-Cl
1j, H
Me
Me
Me
Me
Me
4a, 99
4b, 96
4c, 86
4d, 94
4e, 99
97 (S)
96 (S)
97 (S)
97 (S)
96 (S)
10
11
12
13
1j, H
1k, 4-Me
1l, 3,4-Cl2
1m, 4-NO2
1k, 4-Me
[a] All reactions were carried out with 1 (0.1 mmol), 2a (0.2 mmol) [a] All reactions were carried out with 1 (0.1 mmol), 2b (0.2 mmol),
and 4 Å MS (50 mg) in CH2Cl2 (1.0 mL). [b] Isolated yield. [c] De-
termined by chiral HPLC.
and 4 Å MS (50 mg) in CH2Cl2 (1.0 mL). [b] Isolated yield. [c] De-
termined by chiral HPLC.
Eur. J. Org. Chem. 2012, 183–187
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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185

H.-P. Deng, M. Shi
FULL PAPER
(TMS) as an internal standard. 13C NMR spectra were recorded
with a Bruker AM-300 and AM-400 spectrophotometers (75 or
100 MHz) with complete proton decoupling spectrometers (CDCl3:
77.0 ppm). ) 31P NMR spectra were recorded with a Bruker AM-
400 spectrophotometer (161.94 MHz) with 85% H3PO4 as an in-
ternal standard. Infrared spectra were recorded with a Perkin–El-
mer PE-983 spectrometer. Flash column chromatography was per-
formed by using 300–400 mesh silica gel. For thin-layer chromatog-
raphy (TLC), silica gel plates (Huanghai GF254) were used. Chiral
HPLC was performed with a Shimadzu SPD-10A vp series with
Finally, we examined the scope of the asymmetric allylic
substitution reactions of the MBH carbonates with di-
phenylphosphane oxide (2b) under the optimal conditions
described above. The results are summarized in Table 3.
Once again, regardless of whether there was an electron-
withdrawing or electron-donating substituent on the aro-
matic ring, all of the reactions proceeded smoothly to afford
desired products 4a–e in excellent yields (86–99%) with ex-
cellent enantioselectivities (96–97%ee; Table 3, Entries 1–
5). The absolute configuration of 4a–e was determined to Chiralpak AD-H, OD-H, and IC-H columns 4.6ϫ250 mm,
(Daicel Chemical Ind., Ltd.) and Phenomenex Lux 5μ Amylose-2
column 4.6ϫ250 mm [PA-2, (Phenomenex Ind., Ltd.)] chiral col-
umns. Mass spectra were recorded by EI, ESI, and MALDI tech-
niques and HRMS were measured with a HP-5989 instrument.
be S by X-ray diffraction of 4b bearing a bromine atom on
the benzene ring (Figure 2).[9]
General Procedure for the Preparation of Catalysts: A mixture of
compound II (1.0 equiv.) and amine (2.0 equiv.) in CH2Cl2
(1.0 mL) was stirred at room temperature under an argon atmo-
sphere. After compound II was consumed, the solvent was removed
under reduced pressure, and the residue was purified by flash
chromatography on silica gel (petroleum ether/EtOAc).
1-[(S)-2Ј-(Diphenylphosphanyl)-(1,1Ј-binaphthalen)-2-yl]-3-[(R)-(2-hy-
droxynaphthalen-1-yl)(phenyl)methyl]thiourea (TP10): Following
the general procedure a mixture of compound II (99 mg, 0.2 mmol)
and amine (100 mg, 0.4 mmol) in CH2Cl2 (1.0 mL) provided TP10
as a syrupy oil (123 mg, 83%). [α]2D0 = –75.8 (c = 1.0, CHCl3). IR
(CH Cl ): ν = 3372, 3057, 2926, 1626, 1583, 1519, 1487, 1434, 1330,
˜
2
2
1264, 1216, 1064, 1028, 950, 849, 816, 762, 696, 668 cm–1. 1H NMR
(400 MHz, CDCl3, TMS): δ = 6.62 (d, J = 8.4 Hz, 1 H), 6.83–6.92
(m, 5 H), 6.97–7.12 (m, 8 H), 7.17–7.23 (m, 3 H), 7.27–7.33 (m, 5
H), 7.35–7.40 (m, 5 H), 7.51 (dd, J = 3.2, 8.4 Hz, 1 H), 7.63–7.65
(m, 2 H), 7.75–7.83 (m, 3 H), 7.85–7.88 (m, 2 H), 7.92 (d, J =
8.4 Hz, 1 H), 8.01 (br., 1 H) ppm. 31P NMR (161.94 MHz, CDCl3):
Figure 2. ORTEP representation of the molecular structure of 4b.
δ
= –13.37 ppm. MS (MALDI): m/z (%) = 745.4 (100)
[M + 1]+. HRMS: calcd. for C50H38N2OPS+ [M + 1]+ 745.2437;
found 745.2440.
General Procedure for the Asymmetric Allylic Substitution Reaction
of Morita–Baylis–Hillman Carbonates by Diphenyl Phosphite: A
mixture of 1 (0.1 mmol), 2a (0.2 mmol, 29 mg), TP10 (0.02 mmol,
15 mg), and 4 Å molecular sieves (50 mg) in CH2Cl2 (1 mL) was
stirred at 0 °C under an argon atmosphere. After compound 1 was
completely consumed, the solvent was removed under reduced
pressure, and the residue was purified by flash chromatography on
silica gel (petroleum ether/EtOAc) to provide compound 3.
Conclusions
In summary, we have developed a new method to synthe-
size various chiral multifunctional thiourea–phosphane cat-
alysts from readily available amines. The advantage of this
method is that a wide range of catalysts can be prepared
without the need for functionalized isothiocyanate com-
pounds that tend to be difficult to prepare. Furthermore,
catalyst TP10, derived from precatalyst II and Betti base,
can efficiently catalyze the asymmetric allylic substitution
reactions of MBH carbonates with diphenyl phosphite or
diphenylphosphane oxide, affording the corresponding al-
lylic phosphites in 71–87% yield with 90–97%ee and allylic
phosphane oxides in 86–99% yields with 96–97%ee. Cur-
rently, we are studying the use of the thiourea–phosphane
catalysts in other asymmetric reactions.
Diphenyl
[2-Methylene-1-(4-nitrophenyl)-3-oxobutyl]phosphonate
(3a): Following the general procedure provided 3a as a white solid
(36 mg, 82%). [α]2D0 = +96.1 (c = 1.0, CHCl3). M.p. 135–142 °C. IR
(CH Cl ): ν = 3056, 2929, 1681, 1596, 1523, 1490, 1455, 1422, 1348,
˜
2
2
1266, 1211, 1187, 1162, 1109, 1072, 1025, 1007, 940, 902, 857, 737,
1
703, 653, 633, 614 cm–1. H NMR (400 MHz, CDCl3): δ = 2.35 (s,
3 H, CH3), 5.33 (d, JH,P = 24.0 Hz, 1 H, CH), 6.52 (d, JH,P
3.6 Hz, 1 H, CH), 6.80 (d, J = 8.4 Hz, 2 H, ArH), 6.96 (d, JH,P
=
=
2.8 Hz, 1 H, CH), 7.07–7.11 (m, 3 H, ArH), 7.16–7.20 (m, 3 H,
ArH), 7.29–7.33 (m, 2 H, ArH), 7.72 (dd, J = 2.0, 8.8 Hz, 2 H,
ArH), 8.16 (d, J = 8.8 Hz, 2 H, ArH) ppm. 13C NMR (100 MHz,
CDCl3): δ = 25.2, 42.0 (d, JC,P = 143.1 Hz), 120.1 (d, JC,P
=
Experimental Section
4.3 Hz), 120.3 (d, JC,P = 4.3 Hz), 123.8, 125.3, 125.4, 129.6, 129.8,
129.8, 130.7 (d, JC,P = 8.0 Hz), 141.9 (d, JC,P = 6.0 Hz), 142.8 (d,
JC,P = 1.8 Hz), 143.7 (d, JC,P = 2.6 Hz), 150.0 (d, JC,P = 9.7 Hz),
150.3 (d, JC,P = 9.1 Hz), 196.8 (d, JC,P = 10.8 Hz) ppm. 31P NMR
(161.93 MHz, CDCl3): δ = 16.26 ppm. MS (ESI): m/z (%) = 460.1
(100) [M + Na]+. HRMS (ESI): calcd. for C23H20NNaO6P+ [M +
General Remarks: Melting points were determined with a digital
melting point apparatus. Optical rotations were determined at
589 nm (sodium D line) by using a Perkin–Elmer-341 MC digital
polarimeter. 1H NMR spectra were recorded with a Bruker AM-
300 and AM-400 spectrometer in CDCl3 with tetramethylsilane
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Allylic Phosphites and Phosphane Oxides by Allylic Substitution Reactions
Na]+ 460.0920; found 460.0934. Enantiomeric excess was deter-
mined by HPLC (Chiralcel OD-H column, λ = 214 nm, hexane/
isopropanol = 70:30, flow rate = 0.7 mLmin–1): tR = 17.06 (minor),
20.56 (major) min; ee = 90%.
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cle): Spectroscopic data of all new compounds, detailed descrip-
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Acknowledgments
We thank the Shanghai Municipal Committee of Science and Tech-
nology (08dj1400100–2), the National Basic Research Program of
China [(973)-2010CB833302], and the National Natural Science
Foundation of China (21072206, 20472096, 20872162, 20672127,
20821002, and 20732008) for financial support. Mr. Sun Jie is also
thanked for performing X-ray diffraction studies.
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Received: September 19, 2011
Published Online: November 8, 2011
Eur. J. Org. Chem. 2012, 183–187
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