Highly enantioselective allylation of arylaldehydes catalyzed by a silver(I)-chiral binaphthylthiophosphoramide

Article abstract of DOI:10.1002/ejoc.200300099

Chiral diphenylthiophosphoramide L2 prepared from diphenylthiophosphinic chloride and (R)-(+)-N-ethyl-1,1′-binaphthyl-2,2′-diamine 2 was used as a catalytic chiral ligand in the silver(I)-catalyzed enantioselective allylation reaction of arylaldehydes wit

Full text of DOI:10.1002/ejoc.200300099

FULL PAPER
Highly Enantioselective Allylation of Arylaldehydes Catalyzed by a Silver(
Chiral Binaphthylthiophosphoramide
I
)-
[a]
[a]
Chun-Jiang Wang and Min Shi*
Keywords: Allylation / N,S ligands / Silver / Asymmetric catalysis / Aldehydes
Chiral diphenylthiophosphoramide L2 prepared from di-
phenylthiophosphinic chloride and (R)-(+)-N-ethyl-1,1Ј-bi- to 98%) of the homoallylic alcohols.
naphthyl-2,2Ј-diamine 2 was used as a catalytic chiral ligand ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
in the silver( )-catalyzed enantioselective allylation reaction
of arylaldehydes with allyltributyltin to furnish high ee (up
I
Germany, 2003)
Introduction
scaffold (R)-(ϩ)-1,1Ј-binaphthyl-2,2Ј-diamine by the pro-
cedure shown in Scheme 1. Their structures were deter-
mined using spectroscopic data and microanalysis. Those
chiral ligands (L2ϪL7) were used for the AgOTf-catalyzed
asymmetric allylation reactions of 1-naphthaldehyde and
benzaldehyde. The ees of the products were determined by
HPLC analysis using a chiral stationary-phase column
Catalytic asymmetric synthesis is a valuable method for
preparation of optically active substances.[1] In this connec-
tion, the stereoselective addition of organometallics to one
of the two heterotopic faces of a carbonyl group has been
extensively studied. Among them, the enantioselective al-
lylation of carbonyl compounds is of particular importance
in organic synthesis. Although significant results have been
provided by using a stoichiometric amount of chiral Lewis
(CHIRALCEL OD and OJ) and the absolute configuration
of the major enantiomer was assigned according to the sign
of the specific rotation. The results are summarized in
Table 1. The table shows that L2 (20 mol %) as the chiral
ligand for the silver() (20 mol %)-catalyzed enantioselective
allylation reaction of 1-naphthaldehyde with allyltributyltin
in THF at Ϫ20 °C furnished 76% ee, which is higher that
[
2]
acids, there are only a few methods available for a cata-
lytic process including chiral (acyloxy)borane (CAB) com-
plex/allylic silanes[ or allylic stannanes and binaphthol-
3]
[4]
[
5]
derived chiral titanium complexes/allylic stannanes and
[6]
allylation using BINAP, silver() complex or chiral phos-
[8]
that of L1, in good yield (Table 1, entry 1). Chiral ligands
[
7]
phoramides as a catalyst. Recently, we reported a new
catalytic enantioselective allylation reaction of aldehydes
with allyltributyltin promoted by silver() (AgOTf)-chiral
binaphthylthiophosphoramide L1 derived from (R)-(ϩ)-
L3 and L4 gave the corresponding allylation products in
low ee under the same conditions (Table 1, entries 2 and 3).
Ligand L5 showed no activity for this reaction (Table 1, en-
try 4). Ligands L6 and L7 produced the reaction products
in moderate ee which are very close to that obtained pre-
1,1Ј-binaphthyl-2,2Ј-diamine in which good yields
(65Ϫ84%) and moderate enantioselectivities (54Ϫ63% ee)
[8]
viously with chiral ligand L1 (Table 1, entries 5 and 6).
[8]
have been achieved. In order to get a higher ee in this
Among the solvents examined, THF was the best solvent
for this silver()-chiral ligand-promoted reaction (Table 1,
entries 7Ϫ9). Chiral ligand L2 was also examined for the
allylation reaction of benzaldehyde with allyltributyltin in
the presence of AgOTf. The results are shown in Table 1.
With 20 mol % of L2 and AgOTf (20 mol %), 94% ee was
attained in 84% yield in THF at Ϫ20 °C (Table 1, entry
I
novel Ag -binaphthylthiophosphoramide-catalyzed system,
we have examined ligands similar to L1. Herein, we wish to
report a new ligand, binaphthylthiophosphoramide L2 for
AgOTf-catalyzed allylation of arylaldehydes with allyltribu-
tyltin, in which a high enantioselectivity (up to 98% ee)
was attained.
1
0). At room temperature (20 °C), the enantioselectivity of
allylation product decreased to 73% ee in 28% yield
Table 1, entry 13). We also examined the effect of varying
Results and Discussion
(
The chiral binaphthylthiophosphoramides L1؊L7 in
Figure 1 were synthesized from the C -symmetric chiral
the amount of the catalyst system. However, use of L2 (10
mol %) with AgOTf (10 mol %) or L2 (5 mol %) with Ag-
OTf (5 mol %) decreased the ee to 87% and 68%, respec-
tively (Table 1, entries 11 and 12). In addition, this asym-
metric catalytic system was found to be highly sensitive to
the amount of chiral ligand and AgOTf: no reaction oc-
curred with L2 (20 mol %) and AgOTf (10 mol %) (Table 1,
2
[
a]
State Key Laboratory of Organometallic Chemistry, Shanghai
Institute of Organic Chemistry, Chinese Academy of Sciences
3
54 Fenglin Lu, Shanghai 200032 China
E-mail: mshi@pub.sioc.ac.cn
Supporting information for this article is available on the
WWW under http://www.eurjoc.org or from the author.
Eur. J. Org. Chem. 2003, 2823Ϫ2828
DOI: 10.1002/ejoc.200300099
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2823

C.-J. Wang, M. Shi
FULL PAPER
entry 14). This result suggests that the real active species in L2؊L7 are quite stable organic compounds (Table 2, entry
I
this asymmetric catalytic reaction is an L2:Ag /1:1 chiral 5). As for chiral ligand L2, we believe that it is a bidentate
silver complex.
chiral ligand, with the nitrogen and phosphoryl sulfur
atoms coordinated to the silver() metal affording a chiral
[
10,11]
silver() Lewis acid.
insight into this asymmetric system, we measured the
In order to get more mechanistic
31
P
NMR spectrum of ligand L2 in the absence or presence of
AgOTf. The 31P NMR (CDCl , 85% H PO ) spectrum of
3
3
4
3
1
L2 showed a signal at ϩ53.27 ppm (the P NMR (CDCl3,
5% H PO ) spectrum of L2 with AgOTf (molar ratio, 1:1)
8
3
4
shows a new signal at ϩ58.05 ppm; see Supporting Infor-
Figure 1. The chiral binaphthylthiophosphoramides
mation). This chemical shift clearly indicates the formation
I
of a new Ag -L2 complex, although at present we do not
have a crystal structure for this complex.
The optimized reaction conditions found for the al-
lylation of 1-naphthaldehyde and benzaldehyde (Table 1,
In conclusion, the chiral bidentate phosphoramide L2
entries 1 and 10) were applied to various arylaldehydes. The prepared from C -symmetric (R)-(ϩ)-N-ethyl-1,1Ј-binaph-
2
corresponding homoallylic alcohols could be obtained in thyl-2,2Ј-diamine was found to be a more effective chiral
[
9]
5
6Ϫ80% yield and 68Ϫ98% ee with the S-configuration.
ligand for the silver()-promoted enantioselective allylation
The results are summarized in Table 2. For p-methylbenzal- reaction of arylaldehydes with allyltributyltin than L1.[ In
dehyde and p-chlorobenzaldehyde, 98% and 96% ee were some cases, the corresponding allylation products were ob-
obtained, respectively (Table 2, entries 1 and 2), while trans- tained in Ͼ90% ee by this modified chiral binaphthylthi-
8]
cinnamaldehyde furnished 68% ee (Table 2, entry 4).
ophosphoramide ligand. These results open a new way to
It should be emphasized here that 90% of the chiral phos- design and synthesize new chiral ligands for asymmetric re-
phoramide ligands L2؊L7 could be recovered from the re- actions. We are attempting to elucidate the mechanistic de-
action mixture by column chromatography after the usual tails of this addition reaction and to discover the exact
workup, and could be reused in this asymmetric reaction structure of the active species. Moreover we are planning to
without loss of enantioselectivity because phosphoramides synthesize similar bidentate chiral phosphoramides embed-
Scheme 1
2824
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2003, 2823Ϫ2828

Highly Enantioselective Allylation of Arylaldehydes
FULL PAPER
Table 1. Enantioselective allylation reaction of arylaldehyde in the Experimental Section
presence of chiral ligands L2؊7 and silver() triflate under different
reaction conditions
General Remarks: Melting points were obtained with a Yanagimoto
micro melting point apparatus and are uncorrected. H NMR spec-
1
tra were recorded on a Bruker AM-300 spectrometer in CDCl
3
solution with tetramethylsilane (TMS) as internal standard; J-val-
ues are in Hz. Mass spectra were recorded with a HP-5989 instru-
ment. All of the compounds reported in this paper gave satisfactory
CHN microanalyses with a CarloϪErba 1106 analyzer. Commer-
cially obtained reagents were used without further purification. All
reactions were monitored by TLC with Huanghai GF254 silica-gel
coated plates. Flash column chromatography was carried out using
200Ϫ300 mesh silica gel at increased pressure. Enantiomeric ratios
were determined by chiral HPLC analysis. Racemic products were
synthesized by allylation of aldehydes with allylmagnesium bro-
mide (1.0  in THF) at room temperature.
Synthesis of (R)-(؉)-N-acetyl-1,1Ј-binaphthyl-2,2Ј-diamine (1):
Acetic anhydride (208 µL, 2.2 mmol) was added to a mixture of
(
2
R)-(ϩ)-binaphthyldiamine (568 mg, 2 mmol), acetic acid (1.2 mL,
0 mmol) and dichloromethane (20.0 mL) with ice-cooling. The
mixture was stirred at room temperature overnight, and 2.0 
NaOH was added until pH Ͼ 7. After extraction with dichloro-
methane, the combined organic layers were dried over MgSO . The
4
residue obtained upon evaporation was purified by column chro-
matography to afford 1 as a colorless solid (509 mg, 78%). M.p.
2
5
2
1
40Ϫ241 °C. [α]
675, 1595, 1500, 1445, 1270, 1040, 965, 670 cm
, TMS, 300 MHz): δ ϭ 1.85 (s, 3 H, Me), 6.91Ϫ7.42 (m, 8
H, ArH and NHCO), 7.81Ϫ8.03 (m, 4 H, ArH), 8.58 (d, J ϭ
D 3
ϭ ϩ40.0 (c ϭ 0.55, CHCl
). IR (KBr): ν˜ ϭ 3400,
Ϫ1
1
.
H NMR
[
a]
Isolated yields. [b] Determined by chiral HPLC. [c] The reaction
(CDCl
3
was carried out in the presence of L2 (10 mol %) and AgOTf (10
[
d]
mol %).
The reaction was carried out in the presence of L2 (5
1
3
[e]
9.0 Hz, 2 H, ArH). C NMR [(CD
3
)
2
SO, TMS, 75 MHz]: δ ϭ
mol %) and AgOTf (5 mol %). The reaction was carried out in
the presence of L2 (20 mol %) and AgOTf (10 mol %).
2
1
1
3.98, 110.31, 119.39, 121.93, 123.77, 124.48, 125.01, 125.03,
25.68, 126.18, 126.92, 127.91, 128.66, 128.71, 129.97, 130.03,
32.06, 133.14, 134.51, 136.16, 144.98, 169.53. MS (EI): m/z ϭ 326
ϩ
ϩ
ϩ
(
43) [M ], 284 (M Ϫ 42, 25), 267 (M Ϫ 59, 100). C22H18ON
2
Table 2. Enantioselective allylation reaction of arylaldehyde in the
presence of chiral ligands L2 and silver() triflate under optimized
reaction conditions
(326.39): calcd. C 80.98, H 5.52, N 8.59; found C 80.66, H 5.61,
N 8.48%.
Synthesis of (R)-(؉)-N-Ethyl-1,1Ј-binaphthyl-2,2Ј-diamine (2): A
solution of 1 (509 mg, 1.56 mmol) in 10.0 mL of THF was added
4
dropwise to a stirred suspension of LiAlH (280 mg, 7.37 mmol) in
30.0 mL of anhydrous THF. The mixture was heated under reflux
for 4 h. The reaction mixture was cooled in an ice-bath and the
remaining hydride was carefully quenched by dropwise addition of
water (5.0 mL) and then 10% NaOH (5.0 mL). A white precipitate
was filtered off and thoroughly washed with ethyl acetate. The com-
bined filtrate and ethyl acetate washings were washed with brine
4
and dried over MgSO . After the solvents were evaporated under
reduced pressure, the product was purified by flash chromatogra-
phy to afford product 2 (470 mg, 97%) as a colorless solid. M.p.
2
5
1
3
8
7
23Ϫ124 °C. [α]
D 3
ϭ ϩ175.2 (c ϭ 0.63, CHCl
). IR (KBr): ν˜ ϭ
385, 3060, 2985, 2910, 1645, 1598, 1510, 1425, 1350, 1150, 915,
20 cm . H NMR (CDCl
.5 Hz, 3 H, Me), 3.18 (q, J ϭ 7.5 Hz, 2 H, CH
Ϫ1
1
3
, TMS, 300 MHz): δ ϭ 0.99 (t, J ϭ
), 3.60 (br., 3 H,
2
amino-H), 6.96Ϫ7.25 (m, 8 H, ArH), 7.75Ϫ7.87 (m, 4 H, ArH).
[
a]
Isolated yields. [b] Determined by chiral HPLC. [c] Recovered L2
13
C NMR (CDCl , TMS, 75 MHz): δ ϭ 15.57, 39.02, 112.62,
3
was used as a chiral ligand.
1
1
1
12.84, 114.69, 118.71, 122.28, 122.79, 124.15, 124.36, 127.09,
27.19, 128.03, 128.50, 128.54, 128.80, 129.86, 129.96, 134.01,
ϩ
34.30, 143.35, 144.73. MS (EI): m/z ϭ 313 (M ϩ 1, 100), 297
ϩ
ϩ
ϩ
(
M
Ϫ 15, 34), 280 (M Ϫ 32, 42), 267 (M Ϫ 45, 25). C22
20 2
H N
(
312.41): calcd. C 84.62, H 6.41, N 8.97; found C 84.53, H 6.56,
ded in a C -symmetric chiral scaffold in order to obtain
more effective and stereoselective chiral ligands and to util-
2
N 8.95.
ize those novel chiral ligands in other catalytic asymmetric Synthesis of (R)-(؉)-N-Acetyl-NЈ,NЈ-dimethyl-1,1Ј-binaphthyl-2,2Ј-
reactions. Work along these lines is in progress. diamine (3): A solution of 1 (163 mg, 0.5 mmol) in THF (10 mL)
Eur. J. Org. Chem. 2003, 2823Ϫ2828
www.eurjoc.org
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2825

C.-J. Wang, M. Shi
FULL PAPER
ϩ
and NaBH
4
(133 mg, 3.5 mmol) were simultaneously added to a
SO (0.5 mL) and 40% formaldehyde
121 MHz, 85% H
3
PO
4
): δ ϭ ϩ53.37. MS (EI): m/z ϭ 500 (3) [M ].
stirred solution of 20% H
2
4
C
32
H
25
N
2
PS (500.59): calcd. C 76.78, H 5.03, N 5.60; found C
aqueous solution (0.5 mL, 6.0 mmol) in THF (20 mL) with ice-
cooling over a period of 15 min, the mixture was stirred for an
additional hour and then 1.0  NaOH was added until pH Ͼ 7.
After extraction with ethyl acetate, the combined organic layers
76.65, H 5.07, N 5.74.
Ligand 2 (L2): M.p. 78Ϫ80 °C. [α]2
IR (KBr): ν˜ ϭ 1625, 1600, 1515, 1474, 1426, 1055, 898 cm . 1H
NMR (CDCl , TMS, 300 MHz): δ ϭ 1.11 (t, J ϭ 7.2 Hz, 3 H, Me),
.27 (q, J ϭ 7.2 Hz, 2 H, CH ), 3.78 (br., 1 H, NH), 5.14 (d, J ϭ
.5 Hz, 1 H, NH), 6.95Ϫ7.57 (m, 17 H, ArH), 7.75Ϫ7.91 (m, 5 H,
5
D
3
ϭ Ϫ47.5 (c ϭ 0.905, CHCl ).
Ϫ1
3
4
were dried over MgSO . The residue obtained upon evaporation
3
7
2
was purified by column chromatography to afford 3 as a colorless
solid (108 mg, 61%). M.p. 187Ϫ189 °C. [α]2
5
ϭ Ϫ244.5 (c ϭ 0.58,
D
1
3
ArH). C NMR (CDCl
3
, TMS, 75 MHz): δ ϭ 15.07, 38.42, 109.85,
CHCl
3
1
). IR (KBr): ν˜ ϭ 3402, 1684, 1596, 1501, 1427, 929, 669
1
1
1
5
1
3
13.79, 119.26 (d, J ϭ 4.3 Hz), 119.61 (d, J ϭ 7.8 Hz), 122.01,
Ϫ1
cm . H NMR (CDCl
3
, TMS, 300 MHz): δ ϭ 1.88 (s, 3 H, Me),
.58 (s, 6 H, 2Me), 6.95 (d, J ϭ 8.7 Hz, 1 H, ArH), 7.12Ϫ7.55 (m,
H, ArH), 7.84Ϫ7.80 (m, 4 H, ArH), 8.49 (d, J ϭ 9.0 Hz, 1 H,
23.77, 124.55 (d, J ϭ 57.9 Hz), 126.88, 127.10, 127.45 128.50,
28.51 (d, J ϭ 28.8 Hz), 128.52, 128.67, 128.95, 130.29 (d, J ϭ
1.6 Hz), 130.61 (d, J ϭ 21.4 Hz), 131.63, 131.78, 131.82, 131.84,
31.89, 133.28, 133.46 (d, J ϭ 38.3 Hz), 133.85, 134.83 (d, J ϭ
2
6
13
ArH). C NMR (CDCl
3
, TMS, 75 MHz): δ ϭ 24.85, 43.63,
1
1
1
19.02, 121.81, 124.30, 124.62, 125.02, 125.54, 126.64, 126.67,
26.74, 127.04, 128.17, 128.41, 128.84, 129.90, 130.36, 131.30,
3
1
7.1 Hz), 137.61, 144.51. P NMR (CDCl
PO ): δ ϭ ϩ53.28. MS (EI): m/z ϭ 528 (2) [M ], 311 (M
29 2
17, 1), 267 (M Ϫ 261, 11). C34H N PS (528.65): calcd. C 77.27,
3
, 121 MHz, 85%
ϩ
ϩ
H
2
3
4
Ϫ
33.62, 133.96, 134.12, 149.88, 168.52. MS (EI): m/z ϭ 354 (58)
ϩ
ϩ
ϩ
ϩ
ϩ
[
M ], 311 (M Ϫ 43, 9), 296 (M Ϫ 58, 17), 281 (M Ϫ 73, 36).
O (354.44): calcd. C 81.36, H 6.21, N 7.91; found C
1.40, H 6.39, N 7.80.
H 5.49, N 5.30; found C 77.52, H 5.89, N 5.17.
24 22 2
C H N
Ligand 3 (L3): M.p. 68Ϫ70 °C. [α]2
5
ϭ ϩ30.4 (c ϭ 1.67, CHCl
).
8
D
3
IR (KBr): ν˜ ϭ 3345, 1620, 1598, 1514, 1427, 1345, 994, 926, 669
Synthesis of (R)-(؉)-N,N-dimethyl-1,1Ј-binaphthyl-2,2Ј-diamine (4):
Ϫ1 1
cm . H NMR (CDCl
H, Me), 1.73 (d, J ϭ 12.9 Hz, 3 H, Me), 1.89 (d, J ϭ 12.9 Hz, 3
H, Me), 3.25 (q, J ϭ 7.2 Hz, 2 H, CH ), 3.62 (br., 1 H, NH), 4.61
d, J ϭ 7.2 Hz, 1 H, NH), 6.86 (d, J ϭ 9.3 Hz, 1 H, ArH),
3
, TMS, 300 MHz): δ ϭ 1.09 (t, J ϭ 7.2 Hz,
(
(
(
R)-(ϩ)-N-Acetyl-NЈ,NЈ-dimethyl-1,1Ј-binaphthyl-2,2Ј-diamine
300 mg, 0.85 mmol) was added to a stirred solution of ethanol
25.0 mL) and 4.0  HCl (9.0 mL), the mixture was heated under
3
3
2
(
reflux for 12 h. After cooling to ambient temperature and removal
of the ethanol in vacuo, 2.0  NaOH was added until pH Ͼ 7. After
extraction with dichloromethane, the combined organic layers were
13
7
.01Ϫ7.40 (m, 6 H, ArH), 7.79Ϫ7.99 (m, 5 H, ArH). C NMR
, TMS, 75 MHz): δ ϭ 15.12, 23.96 (d, J ϭ 68.9 Hz), 24.81
d, J ϭ 68.6 Hz), 38.29, 109.60, 113.68, 118.89, 118.94, 119.61,
(CDCl
3
(
4
dried over MgSO . The residue obtained upon evaporation was
1
1
21.91, 123.35, 124.22, 124.94, 126.89, 126.94, 127.22, 128.19,
29.13, 129.99, 130.42, 133.26, 133.66, 137.83, 144.34. P NMR
purified by column chromatography to afford 4 as a colorless solid
31
2
5
(
262 mg, 99%). M.p. 116Ϫ118 °C. [α]
D 3
ϭ ϩ17.4 (c ϭ 2.0, CHCl ).
(
(
(
CDCl
100) [M ], 389 (M Ϫ 15, 5), 267 (M Ϫ 137, 25). C24
404.51): calcd. C 71.29, H 6.19, N 6.93; found C 71.65, H 6.57,
3 3 4
, 121 MHz, 85% H PO ): δ ϭ ϩ56.62. MS (EI): m/z ϭ 404
IR (KBr): ν˜ ϭ 3395, 2794, 1621, 1507, 1426, 1380, 1143, 989, 930,
ϩ
ϩ
ϩ
25 2
H N PS
Ϫ1
1
6
25 cm . H NMR (CDCl
3
, TMS, 300 MHz): δ ϭ 2.59 (s, 2Me),
7
(
.0Ϫ7.29 (m, 7 H, ArH), 7.47 (d, J ϭ 9.0 Hz, 1 H, ArH), 7.74Ϫ7.91
N 6.49.
Ligand 4 (L4): M.p. 180Ϫ182 °C. [α]2
IR (KBr): ν˜ ϭ 3350, 1620, 1514, 1476, 1422, 927, 626 cm . H
m, 4 H, ArH). 1 C NMR (CDCl
3
, TMS, 75 MHz): δ ϭ 38.47,
3
5
D
3
ϭ ϩ65.8 (c ϭ 0.6, CHCl ).
1
1
1
11.70, 113.46, 114.65, 117.12, 117.17, 118.75, 119.91, 119.99,
21.36, 121.62, 122.98, 123.03, 123.32, 123.91, 124.28, 124.90,
Ϫ1
1
ϩ
NMR (CDCl , TMS, 300 MHz): δ ϭ 1.76 (d, J ϭ 13.5 Hz, 3 H,
28.71, 129.27, 136.94, 145.23. MS (EI): m/z ϭ 312 (100) [M ], 297
3
ϩ
ϩ
ϩ
Me), 1.88 (d, J ϭ 13.5 Hz, 3 H, Me), 4.61 (d, J ϭ 6.6 Hz, 1 H,
NH), 6.96 (d, J ϭ 8.1 Hz, 1 H, ArH), 7.13Ϫ7.40 (m, 6 H, ArH),
(M
Ϫ 15, 4), 280 (M Ϫ 32, 38), 267 (M Ϫ 45, 47). C22
20 2
H N
(312.41): calcd. C 84.62, H 6.41, N 8.97; found C 84.70, H 6.55,
1
3
7
2
1
1
1
3
.80Ϫ7.99 (m, 5 H, ArH). C NMR (CDCl , TMS, 75 MHz): δ ϭ
4.01 (d, J ϭ 68.6 Hz), 24.60 (d, J ϭ 68.6 Hz), 110.16, 118.08,
18.97, 119.03, 122.54, 123.57, 124.25, 124.91, 126.95, 127.07,
N 8.92.
Representative Experimental Procedure for the Synthesis of Ligands
1؊8: n-Butyllithium (1.12 mL, 1.8 mmol, 1.6  solution in hexane)
28.09, 128.19, 128.21, 129.15, 129.97, 130.26, 133.04, 133.58,
was added dropwise to a solution of (R)-(ϩ)-N-ethyl-1,1Ј-binaph-
thyl-2,2Ј-diamine 2 (200 mg, 0.64 mmol) in THF (10.0 mL) at Ϫ40
31
3 3 4
37.62, 142.86. P NMR (CDCl , 121 MHz, 85% H PO ): δ ϭ
ϩ
ϩ
ϩ56.96. MS (EI): m/z ϭ 376 (49) [M ], 284 (M Ϫ 92, 16), 267
°
C over 40 min, and the reaction mixture was stirred for 1 h at the
same temperature. Then diphenylthiophosphinic chloride (500 mg,
.0 mmol) in THF (5.0 mL) was added dropwise and the reaction
ϩ
(
21 2
M Ϫ 109, 100). C22H N PS (376.46): calcd. C 70.19, H 5.62, N
7.44; found C 69.84, H 5.82, N 7.65.
2
Ligand 5 (L5): M.p. 62Ϫ64 °C. [α]2
IR (KBr): ν˜ ϭ 3350, 3054, 1619, 1595, 1507, 1438, 1422, 1338,
5
ϭ Ϫ180.1 (c ϭ 1.83, CHCl
).
D
3
solution was slowly warmed to room temperature. After 2 h, THF
was removed in vacuo. The residue was purified by alumina column
chromatography to give the ligand 2 (L2) as a colorless solid
Ϫ1
1
1
219, 1153, 896, 817 cm
δ ϭ 2.53 (s, 6 H, 2Me), 5.88 (d, J ϭ 9.0 Hz, NH), 7.0 (d, J ϭ
.7 Hz, 1 H, Ar), 7.14Ϫ7.43 (m, 12 H, ArH), 7.56Ϫ7.75 (m, 5 H,
3
. H NMR (CDCl , TMS, 300 MHz):
(314 mg, 93%).
8
Ligand 1 (L1): M.p. 175Ϫ177 °C. [α]25
ϭ Ϫ4.0 (c ϭ 1.20, CHCl
IR (KBr): ν˜ ϭ 3350, 1625, 1514, 1477, 1438, 1340, 929, 634 cm
).
.
ArH), 7.79Ϫ7.98 (m, 4 H, ArH). C NMR (CDCl
75 MHz): δ ϭ 43.27, 118.47, 120.41 (d, J ϭ 4.8 Hz), 121.81, 123.92
, TMS, 300 MHz): δ ϭ 4.10 (br. s, 2 H, NH), 5.12 (d, J ϭ 2.6 Hz), 125.75, 126.56 (d, J ϭ 8.3 Hz), 125.97, 128.34 (d,
d, J ϭ 7.4 Hz, 1 H, NH), 7.0Ϫ7.50 (m, 10 H, ArH), 7.50Ϫ7.70 (m, J ϭ 18.6 Hz), 128.36, 128.37 (d, J ϭ 24.0 Hz), 128.38 (d, J ϭ
13
D
3
Ϫ1
3
, TMS,
1
H NMR (CDCl
3
(
4
7
4
5
1
H, ArH), 7.70Ϫ8.0 (m, 8 H, ArH). 13C NMR (CDCl
5 MHz): δ ϭ 110.39, 118.25 (d, J ϭ 4.4 Hz), 119.28 (d, J ϭ
.8 Hz), 119.84 (d, J ϭ 8.9 Hz), 122.67, 124.00, 124.54 (d, J ϭ
1.7 Hz), 127.12 (d, J ϭ 27.8 Hz), 127.26, 128.28, 128.33, 128.52,
3
, TMS, 47.7 Hz), 128.41, 129.67, 129.84 (d, J ϭ 2.8 Hz), 131.04, 131.20,
131.48, 131.52, 131.57, 131.68, 131.72, 132.99, 133.88, 134.03,
3
1
134.04 (d, J ϭ 46.1 Hz), 135.25, 136.59, 149.87. P NMR (CDCl
3
,
121 MHz, 85% H PO ): δ ϭ ϩ51.47. MS (EI): m/z ϭ 528 (46)
3
4
ϩ
ϩ
ϩ
28.71, 128.95, 130.01 (d, J ϭ 27.9 Hz), 130.80, 130.95, 131.62 (d, [M ], 311 (M Ϫ 217, 35), 267 (M Ϫ 261, 100). C34
(528.65): calcd. C 77.27, H 5.49, N 5.30; found C 77.29, H 5.68,
N 5.12.
29 2
H N PS
J ϭ 11.5 Hz), 131.82, 131.86, 131.90, 133.15, 133.41 (d, J ϭ
5
1.5 Hz), 133.57, 134.52, 134.93, 137.35, 143.16. 31P NMR (CDCl
,
3
2826
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2003, 2823Ϫ2828

Highly Enantioselective Allylation of Arylaldehydes
FULL PAPER
Ligand 6 (L6): M.p. 61Ϫ63 °C. [α]25
ϭ ϩ41.3 (c ϭ 2.07, CHCl
IR (KBr): ν˜ ϭ 3020, 1625, 1600, 1521, 1750, 1423, 1030, 929, 895
).
those reported in literature.[6b] 1H NMR (CDCl
δ ϭ 2.36 (br., 1 H, OH), 2.48 (m, 2 H, CH ), 4.68 (m, 1 H, CH),
3
, TMS, 300 MHz): δ ϭ 1.28 (m, 6 H, 2Me), 5.13 (m, 2 H, vinyl H), 5.78 (m, 1 H, vinyl H), 7.31 (m, 5 H, ArH).
D
3
3
, TMS, 300 MHz):
2
Ϫ1
1
cm . H NMR (CDCl
2
5
[6b]
25
3
1
6
7
.69 (br., 2 H, NH
4.1 Hz, 1 H, NH), 6.91 (d, J ϭ 8.1 Hz, 1 H, ArH), 7.12Ϫ7.37 (m,
H, ArH), 7.80Ϫ7.96 (m, 5 H, ArH). 13C NMR (CDCl
, TMS, 0.7 mL/min, 254 nm, t
5 MHz): δ ϭ 15.61 (d, J ϭ 8.4 Hz), 15.64 (d, J ϭ 7.4 Hz), 63.19
2
), 3.97Ϫ4.17 (m, 4 H, 2CH
2
), 5.32 (d, J ϭ [α]
(c ϭ 1.1, benzene) for 96% ee}; Chiralcel OD, hexane/iPrOH (95:5),
ϭ 13.44 min, t ϭ 15.87 min.
D
ϭ Ϫ45.5 (c ϭ 2.6, benzene) for 94% ee {ref.
D
[α] ϭ Ϫ50.5
3
R
S
(
S)-(؊)-1-(1-Naphthyl)-3-buten-1-ol: (Table 1, entry 1) This is a
(d, J ϭ 4.1 Hz), 63.23 (d, J ϭ 4.6 Hz), 110.08, 117.92, 117.96,
1
known compound and H NMR spectroscopic data are in agree-
1
1
1
18.00, 118.04, 118.07, 122.44, 123.29, 124.12, 124.93, 126.84,
27.90, 128.15, 129.17, 129.75, 130.23, 132.83, 133.48, 136.31,
ment with those reported in literature.[
6b] 1
H NMR (CDCl
00 MHz): δ ϭ 2.36 (d, J ϭ 3.0 Hz, 1 H, OH), 2.61 (m, 1 H, CH),
.76 (m, 1 H, CH), 5.21 (m, 2 H, vinyl H), 5.55 (m, 1 H, CH), 5.94
3
, TMS,
3
2
42.70. 31P NMR (CDCl
, 121 MHz, 85% H PO ): δ ϩ66.63. MS
3 3 4
ϩ
ϩ
ϩ
(
EI): m/z ϭ 436 (77) [M ], 284 (M Ϫ 152, 52), 267 (M Ϫ 169,
00). C24 PS (436.51): calcd. C 66.10, H 5.73, N 6.42;
found C 65.91, H 6.03, N 6.51.
(
m, 1 H, vinyl H), 7.52 (m, 3 H, ArH), 7.68 (d, J ϭ 7.2 Hz, 1 H,
1
25 2 2
H N O
ArH), 7.79 (d, J ϭ 8.1 Hz, 1 H, ArH), 7.89 (m, 1 H, ArH), 8.08
2
5
(
d, J ϭ 7.8 Hz, 1 H, ArH). [α]
D
ϭ Ϫ69.9 (c ϭ 1.7, benzene) for
Ligand 7 (L7): Yellowish oil, [α]25
76% ee {ref.
alcel OD, hexane/iPrOH (90:10), 0.7 mL/min, 254 nm, t
13.97 min, t ϭ 22.50 min.
[6b] [α]25 ϭ Ϫ96.0 (c ϭ 1.1, benzene) for 97% ee}; Chir-
D
ϭ ϩ13.7 (c ϭ 2.57, CHCl
3
). IR
D
(
KBr): ν˜ ϭ 3360, 3020, 1630, 1598, 1514, 1476, 1427, 1346, 1022,
R
ϭ
Ϫ1
1
9
64, 801 cm . H NMR (CDCl
3
, TMS, 300 MHz): δ ϭ 1.06 (t,
),
), 5.31 (d, J ϭ
3.2 Hz, 1 H, NH), 6.81 (d, J ϭ 8.4 Hz, 1 H, ArH), 7.08Ϫ7.36 (m,
H, ArH), 7.78Ϫ7.96 (m, 5 H, ArH). 13C NMR (CDCl
, TMS,
S
J ϭ 6.9 Hz, Me), 1.28 (m, 6 H, 2Me), 3.24 (q, J ϭ 6.9 Hz, CH
2
(
S)-(؊)-1-(p-Tolyl)-3-buten-1-ol: (Table 2, entry 1) This is a known
3
1
6
7
3
1
1
1
.51 (br., 1 H, NH), 3.95Ϫ4.13 (m, 4 H, 2CH
2
1
compound and H NMR spectroscopic data are in agreement with
[9] 1
those reported in literature. H NMR (CDCl
δ ϭ 2.0 (br., 1 H, OH), 2.35 (s, 3 H, CH ), 2.49 (m, 2 H, CH
.71 (m, 1 H, CH), 5.15 (m, 2 H, vinyl H), 5.81 (m, 1 H, vinyl H),
.17 (d, J ϭ 7.8 Hz, 2 H, ArH), 7.27 (d, J ϭ 7.8 Hz, 2 H, ArH).
3
, TMS, 300 MHz):
3
3
2
),
5 MHz): δ ϭ 15.10, 15.73 (d, J ϭ 7.9 Hz), 15.77 (d, J ϭ 7.9 Hz),
8.32, 63.27 (d, J ϭ 4.8 Hz), 63.30 (d, J ϭ 4.2 Hz), 109.70, 113.88,
18.10, 118.13, 121.91, 123.20, 124.21, 125.13, 126.80, 126.92,
27.41, 127.99, 128.23, 129.28, 129.92, 130.46, 133.22, 133.65,
4
7
25
[9]
25
[α]
D
ϭ Ϫ47.1 (c ϭ 1.5, benzene) for 98% ee {ref. [α]
c ϭ 2.0, benzene) for 82% ee}; Chiralpak AD, hexane/iPrOH
98:2), 0.7 mL/min, 254 nm, t ϭ 21.12 min, t ϭ 23.54 min.
D
ϭ Ϫ37.3
(
(
36.64, 144.38. 31P NMR (CDCl
3 3 4
, 121 MHz, 85% H PO ): δ ϭ
R
S
ϩ
ϩ
ϩ66.57. MS (EI): m/z ϭ 464 (100) [M ], 311 (M Ϫ 153, 25),
ϩ
ϩ
2
4
67 (M Ϫ 197, 70). HRMS: calcd. for C26
H
30
N
2
O
2
PS (M ϩ1) (S)-(؊)-1-(p-Chlorophenyl)-3-buten-1-ol: (Table 2, entry 2) This is a
1
65.1756; found 465.1760.
known compound and H NMR spectroscopic data are in agree-
ment with those reported in literature.[ H NMR (CDCl
9] 1
, TMS,
), 4.72 (m,
H, CH), 5.18 (m, 2 H, vinyl H), 5.79 (m, 1 H, vinyl H), 7.31 (m,
3
Ligand 8 (L8): M.p. 57Ϫ58 °C. [α]25
IR (KBr): ν˜ ؍ 3350, 3020, 1619, 1598, 1517, 1475, 1424, 1378,
D
3
ϭ Ϫ149.1 (c ϭ 0.9, CHCl ).
3
1
4
00 MHz): δ ϭ 2.15 (br., 1 H, OH), 2.47 (m, 2 H, CH
2
Ϫ1
1
1
216, 1045, 929, 811 cm
δ ϭ 1.07 (t, J ϭ 7.2 Hz, 3 H, Me), 3.25 (q, J ϭ 7.2 Hz, 2 H, CH
.75 (br., 1 H, NH), 5.46 (d, J ϭ 10.8 Hz, 1 H, NH), 6.98Ϫ7.49
.
H NMR (CDCl
3
, TMS, 300 MHz):
25
[9]
H, ArH). [α]
D
ϭ Ϫ23.5 (c ϭ 2.1, benzene) for 96% ee {ref.
ϭ Ϫ28.4 (c ϭ 3.03, benzene) for 84% ee}; Chiralcel OJ, hexane/
iPrOH (97.5:2.5), 0.7 mL/min, 254 nm, t ϭ 33.40 min, t
6.11 min.
),
23
2
[α]
D
3
S
R
ϭ
13
(
m, 15 H, ArH), 7.64Ϫ7.94 (m, 7 H, ArH). C NMR (CDCl
TMS, 75 MHz): δ ϭ 14.77, 38.48, 113.90, 118.40 (d, J ϭ 8.7 Hz),
19.13 (d, J ϭ 4.4 Hz), 122.16 (d, J ϭ 3.3 Hz), 124.11, 124.32 (d,
J ϭ 84.3 Hz), 126.97 (d, J ϭ 5.9 Hz), 127.54, 127.63, 128.25,
3
,
3
(
S)-(؊)-1-(p-Methoxyphenyl)-3-buten-1-ol: (Table 2, entry 3) This is
1
1
a known compound and H NMR spectroscopic data are in agree-
ment with those reported in literature.[
6b] 1
H NMR (CDCl
, TMS,
1
1
1
28.33, 128.98 (d, J ϭ 71.4 Hz), 128.66, 128.68, 129.41, 129.88,
30.35, 130.96, 131.19 (d, J ϭ 10.3 Hz), 131.50, 131.89, 131.98,
3
300 MHz): δ ϭ 2.09 (br., 1 H, OH), 2.51 (m, 2 H, CH
2
), 3.81 (s, 3
3
1
H, CH ), 4.69 (m, 1 H, CH), 5.14 (m, 2 H, vinyl H), 5.79 (m, 1 H,
32.02, 132.68, 133.21, 133.52, 137.66, 144.32 (d, J ϭ 2.3 Hz).
, 121 MHz, 85% H PO ): δ ϭ ϩ17.89. MS (EI):
m/z ϭ 512 (53) [M ], 497 (M Ϫ 15, 12), 295 (M Ϫ 217, 92), 280
P
3
vinyl H), 6.88 (d, J ϭ 8.7 Hz, 2 H, ArH), 7.27 (d, J ϭ 8.7 Hz, 2
NMR (CDCl
3
3
4
2
5
[6b]
25
ϩ
ϩ
ϩ
3 D
H, ArH). [α]D ϭ Ϫ42.5 (c ϭ 1.1, CHCl ) for 80% ee {ref. [α] ϭ
ϩ
ϩ
Ϫ40.7 (c ϭ 1.1, benzene) for 97% ee}; Chiralcel OD, hexane/iPrOH
(M
Ϫ 232, 39). HRMS: calcd. for C34
29 2
H N OP [M ] 520.2017;
(
20:1), 0.7 mL/min, 254 nm, t
R S
ϭ 8.60 min, t ϭ 9.11 min.
found 520.2061.
(
S), (E)-(؊)-1-Phenyl-3-buten-1-ol: (Table 2, entry 4) This is a
General Procedure for the AgOTf-Catalyzed Asymmetric Allylation
of Arylaldehydes: Under argon atmosphere and in the dark, AgOTf
1
known compound and H NMR spectroscopic data are in agree-
ment with those reported in literature.[
6b] 1
H NMR (CDCl
00 MHz): δ ϭ 1.92 (br., 1 H, OH), 2.41 (m, 2 H, CH ), 4.35 (m,
H, CH), 5.17 (m, 2 H, vinyl H), 5.83 (m, 1 H, vinyl H), 6.24 (dd,
3
, TMS,
(
26 mg, 0.1 mmol) and L2 (53 mg, 0.1 mmol) were dissolved in dry
THF (2 mL) and stirred for 30 min at 0 °C. Benzaldehyde (51 µL,
.5 mmol) and allyltributylstannane (186 µL, 0.6 mmol) were ad-
3
1
2
0
J ϭ 6.6, 16.2 Hz, 1 H, vinyl H), 6.60 (d, J ϭ 16.2 Hz, 1 H, vinyl
ded successively to the resulting solution at Ϫ20 °C, the mixture
was stirred for 48 h at this temperature, then treated with saturated
KF solution, and extracted with diethyl ether. The combined or-
2
5
H), 7.33 (m, 5 H, ArH). [α]
D
ϭ ϩ10.6 (c ϭ 1.3, diethyl ether) for
ϭ ϩ15.4 (c ϭ 1.1, diethyl ether) for 88% ee};
Chiralcel OD, hexane/iPrOH (20:1), 0.7 mL/min, 254 nm, t
9.32 min, t ϭ 32.73 min.
8% ee {ref.[ [α]
6b]
25
6
D
R
ϭ
4
ganic layers were dried over MgSO and the solvent was removed
1
S
in vacuo. The residue was purified by column chromatography to
give the homoallylic alcohol (62 mg, 84% yield) as a colorless oil.
The enatioselectivity was determined to be 94% ee by HPLC analy-
sis. The chiral HPLC charts are given in the Supporting Infor-
mation (see also the footnote on the first page of this article).
Acknowledgments
We thank the State Key Project of Basic Research (Project 973)
(
No. G2000048007), Shanghai Municipal Committee of Science
(
S)-(؊)-1-Phenyl-3-buten-1-ol: (Table 1, entry 10) This is a known
and Technology, and the National Natural Science Foundation of
China (20025206 and 20272069) for financial support.
1
compound and H NMR spectroscopic data are in agreement with
Eur. J. Org. Chem. 2003, 2823Ϫ2828
www.eurjoc.org
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2827

C.-J. Wang, M. Shi
FULL PAPER
H. Nakashima, A. Ishiba, H. Yamamoto, Bull. Chem. Soc. Jpn.
[
1] [1a]
I. Ojima (Ed.), Catalytic Asymmetric Synthesis. VCH Pub-
2
001, 74, 1129Ϫ1137.
lishers: Cambridge, 1993. [ R. Noyori, Asymmetric Catalysis
in Organic Synthesis; John Wiley & Sons: New York, 1994. [
R. E. Gawley, J. Aube, Principles of Asymmetric Synthesis
1b]
[7] [7a]
S. E. Demark, D. M. Coe, N. E. Pratt, B. D. Griedel, J.
1c]
[7b]
Org. Chem. 1994, 59, 6161Ϫ6163.
J. Am. Chem. Soc. 2001, 123, 6199Ϫ6200.
S. E. Demark, T. Wynn,
(
Eds.: J. E. Baldwin, P. D. Magnus); Pergamon: Oxford, 1996.
[8]
[9]
M. Shi, W. -S. Sui, Tetrahedron: Asymmetry 2000, 11, 773Ϫ779.
N. Minowa, T. Mukaiyama, Bull. Chem. Soc., Jpn. 1987, 60,
[
1d]
N. Jacobsen, A. Pfaltz, H. Yamamoto, Comprehensive
Asymmetric Catalysis, 1999, Springer-Verlag, Berlin.
3
697Ϫ3704.
[
[
2]
[2a]
[10]
For several reviews on asymmetric allylation, see: [ Y. Ya m a -
Previously we found that this allylation reaction could take
place only when the heteroatom on the phosphorus atom was
a sulfur atom; if it was an oxygen atom, no reaction could take
place. This result strongly suggests that coordination between
the sulfur atom and silver() metal plays an important role in
2b]
moto, N. Asao, Chem. Rev. 1993, 93, 2207Ϫ2293.
T. Bach,
Angew. Chem. Int. Ed. Engl. 1994, 33, 417Ϫ419. [ A. H. Hov-
2c]
eyda, J. P. Morken, Angew. Chem. Int. Ed. Engl. 1996, 35,
1
262Ϫ1284.
this reaction.[ For selected X-ray crystal structures of Cu com-
8]
3] [3a]
K. Furuta, M. Mouri, H. Yamamoto, Synlett 1991,
plexes coordinated by S, N ligands, see: [
10a]
D. M. Koten, D.
[
3b]
5
61Ϫ562.
K. Furuta, H. Yamamoto, J. Am. Chem. Soc. 1993, 115,
1490Ϫ11495.
J. A. Marshall, Y. Tang, Synlett 1992, 653Ϫ654.
K. Ishihara, M. Mouri, Q. Gao, T. Maruyama,
M. Grove, W. J. Smeets, A. L. Spek, G. van Koten, J. Am.
Chem. Soc. 1992, 114, 3400Ϫ3410. [
Brown, M. K. Yoo, T. M. Kutchan, E. A. Mottel, Inorg. Chem.
979, 18, 299Ϫ302.
10b]
G. R. Brubaker, J. N.
1
[
[
4]
1
5] [5a]
S. Aoki, K. Mikami, M. Tetrada, T. Nakai, Tetrahedron
[11]
[11a]
For chiral ligands with a sulfur atom, see:
E. J. Miller, T.
993, 49, 1783Ϫ1792. [ A. L. Costa, M. G. Piazza, E. Tag-
5b]
1
B. Brill, A. L. Rheingold, W. C. Fultz, J. Am. Chem. Soc. 1983,
liavini, C. Trombini, A. Umani-Ronchi, J. Am. Chem. Soc.
[11b]
1
05, 7580Ϫ7584.
sti, Synlett 1993, 833Ϫ834.
Chem. Pharm. Bull. 1995, 43, 2243Ϫ2244.
Satoh, T. Makihara, M. Shi, Chem. Pharm. Bull. 1996, 44,
G. Jommi, R. Pagliarin, G. Rizzi, M. Si-
993, 115, 7001Ϫ7002. [ G. E. Keck, K. H. Tarbet, L. S.
5c]
1
[11c]
Y. Arai, N. Nagata, Y. Masaki,
[5d]
Geraci, J. Am. Chem. Soc. 1993, 115, 8467Ϫ8468.
G. E.
[11d]
Y. Masaki, Y.
Keck, L. S. Geraci, Tetrahedron Lett. 1993, 34, 7827Ϫ7828. [
5e]
G. E. Keck, D. Krishnamurthy, M. C. Grier, J. Org. Chem.
[11e]
4
54Ϫ456.
J. Priego, O. G. Mancheno, S. Cabrera, R. G.
1
993, 58, 6543Ϫ6544.
Arrayas, T. Llamas, J. C. Carretero, Chem. Commun. 2002,
2512Ϫ2513 and references cited therein.
Received February 17, 2003
[
6] [6a]
A. Yanagisawa, H. Nakashima, A. Ishiba, H. Yamamoto,
J. Am. Chem. Soc. 1996, 118, 4723Ϫ4724. [ A. Yanagisawa,
6b]
2828
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2003, 2823Ϫ2828