Chiral phosphine-catalyzed regio- and enantioselective allylic amination of Morita-Baylis-Hillman acetates

Article abstract of DOI:10.1016/j.tetasy.2009.03.040

Enantioselective allylic substitution of Morita-Baylis-Hillman (MBH) acetates with phthalimide was realized in the presence of a novel l-proline-derived chiral trifunctional phosphine amide ligand to give the corresponding allylic amination adducts in goo

Full text of DOI:10.1016/j.tetasy.2009.03.040

Tetrahedron: Asymmetry 20 (2009) 1086–1092
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Tetrahedron: Asymmetry
journal homepage: www.elsevier.com/locate/tetasy
Chiral phosphine-catalyzed regio- and enantioselective allylic amination
of Morita–Baylis–Hillman acetates
Guang-Ning Ma a, Shu-Hua Cao a, Min Shi a,b,
*
a Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and Technology,
130 MeiLong Road, Shanghai 200237, China
b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 18 February 2009
Accepted 23 March 2009
Enantioselective allylic substitution of Morita–Baylis–Hillman (MBH) acetates with phthalimide was
realized in the presence of a novel L-proline-derived chiral trifunctional phosphine amide ligand to give
the corresponding allylic amination adducts in good yields (70–95%) and in modest to good enantioselec-
tivities (34–78% ee’s).
Ó 2009 Elsevier Ltd. All rights reserved.
1. Introduction
oselectivities and in good yields, respectively.8a,b These organocat-
alysts-promoted allylic substitutions exhibited exceptionally high
The Morita–Baylis–Hillman (MBH) reaction1 provides a conve-
nient and atom-economic synthetic method for the preparation
levels of regiospecificity by virtue of a tandem SN20/SN20 mecha-
nism. To the best of our knowledge, only one asymmetric version
of this allylic amination catalyzed by a chiral phosphine has been
reported by Hou et al. using planar chiral [2,2]paracyclophane
monophosphines to provide the allylic amination products in high
regioselectivities and in modest enantioselectivities (9–71% ee’s).9
Their experimental data revealed that the MBH acetates derived
from alkyl acrylates gave the allylic amination products in higher
enantioselectivities (21–71% ee’s), whereas, the MBH acetates de-
rived from methyl vinyl ketone (MVK) afforded the allylic amina-
tion products in rather lower enantioselectivities (10–17% ee’s).
To further extend the substrate scope of this phosphine-catalyzed
successive SN20/SN20 reaction, we herein report a variety of chiral
phosphine- and chiral phosphine-amide ligand-catalyzed asym-
metric allylic aminations by using MVK-derived MBH acetates as
substrates to give the corresponding adducts in up to 78% ee and
good yields.
of
b-hydroxy-
a-methylene-carbonyl-containing
compounds,
which have proven to be valuable synthetic intermediates in fur-
ther chemical transformations2 since great progress has been made
in the execution of these MBH adducts over the last decade.3 For
example, Pd-catalyzed asymmetric allylic alkylation and amination
of MBH adducts, as well as the application in the synthesis of sev-
eral complex natural products, have been reported by Trost4a–d and
Hamada,4e respectively. On the other hand, the transformation of
MBH adducts via direct substitution reactions by using nucleo-
philic nitrogen-containing organocatalysts has also been devel-
oped. For example, the amination of MBH acetates mediated by
stoichiometric amounts of 1,4-diazabicyclo[2,2,2]octane (DABCO)
was reported by Kim et al.5 Moreover, Orena et al. recently re-
ported DABCO-catalyzed regioselective allylic amination of MBH
products to give the unsaturated b-aminoacid derivatives in good
yields.6 Later on, alkaloid-catalyzed asymmetric versions of
the allylic substitution reaction of MBH adducts with
a
2. Results and discussion
variety of nucleophiles have been extensively disclosed using
(DHQD)2PHAL,5b quinidine,7a brucine,7b and other Cinchona alka-
loid derivatives,7b,c to afford the corresponding allylic amination
or alkylation products in good yields and in modest to good
enantioselectivities.
In 2004, Krische and co-workers reported the first example of
phosphine-catalyzed intermolecular allylic substitution reactions
of MBH acetates, wherein N- and C-nucleophiles such as 4,5-
dichlorophthalimide and 2-trimethylsilyloxyfuran (TMSOF) were
The chiral phosphine nucleophilic catalysts for the allylic sub-
stitution reaction are shown in Scheme 1. The monophosphine cat-
alysts MOP1 and MOP2,10 the bifunctional phosphine catalysts
BP1–4 (one phenolic hydroxyl group and one phosphorus atom),11
and bifunctional phosphine-amide ligands BPA1–4 (one amide
group and one phosphorus atom)12 were synthesized by the previ-
ously reported procedures. The chiral trifunctional phosphine-
amide catalyst (aR,S)-TPA1 (one amide group, one phosphorus
atom, and one amino group) was prepared by reacting (R)-(ꢀ)-
2-(diphenylphoshino)-1,10-binaphthyl-20-amine11 with N-Boc-
utilized to generate allylic amines and c-butenolides in high regi-
L
-proline at room temperature in the presence of 1,3-dicyclohexyl-
* Corresponding author. Tel.: +86 21 54925137; fax: +86 21 64166128.
E-mail address: Mshi@mail.sioc.ac.cn (M. Shi).
carbodiimide (DCC) and a catalytic amount of N,N-dimethylamino-
0957-4166/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetasy.2009.03.040

G.-N. Ma et al. / Tetrahedron: Asymmetry 20 (2009) 1086–1092
1087
NR1R2
PPh2
OH
R
PR1R2
PPh2
1
2
BPA1: R1 = H, R2 = Ac
BPA2: R1 = H, R2 = Ts
BPA3: R1 = H, R2 = Tf
BPA4: R1 = R2 = Ac
BP1
BP2
: R1 = R = Ph
MOP1: R = H
2
: R = Ph, R = Et
MOP2
: R = OMe
BP3: R1 = Ph, R2 = nBu
BP4: R1 = R2 = Cy
O
1) N-Boc-L-proline (1.5 eq.)
DCC (1.5 eq.), DMAP (cat.)
CH2Cl2, rt, 72 h
NH2
(S)
HN
N
H
(R)
2)
TFA/CH2Cl2 (v/v = 1:4), rt, 5 h
3) NH3 (aq.) pH > 8
PPh2
PPh2
(aR,S)-TPA1
65% (3 stepsoverallyield)
Ph2P
Ph2P
H
H
(R)
(R)
N
N
(S)
N
(R)
N
H
Boc
O
O
(aR,S)-N-Boc-TPA1
(aR,R)-TPA2
Scheme 1. Chiral monophosphines MOP1 and MOP2, bifunctional phosphines BP1-4, bifunctional phosphine-amide catalysts BPA1-4, and the synthesis of trifunctional
phosphine-amide catalysts (aR,S)-TPA1, (aR,S)-N-Boc-TPA1, (aR,R)-TPA2.
pyridine (DMAP) as the condensation agents give the correspond-
ing N-protected organocatalyst (aR,S)-N-Boc-TPA1. Then, the N-
Boc protecting group was removed by typical method, and basified
with aqueous ammonia solution to pH > 8, affording (aR,S)-TPA1 li-
gand in 65% overall yield in three steps. Moreover, (aR,R)-TPA2 was
synthesized from the reaction of (R)-(ꢀ)-2(diphenylphosphino)-
on the phosphorus atom showed a lower catalytic activity (Table
1, entry 6). Chiral phosphine-amide catalysts were also studied un-
der similar conditions. The bifunctional phosphine-amide catalysts
BPA1 (R1 = H, R2 = Ac) and BPA2 (R1 = H, R2 = Ts) afforded product
3a in good yields and in modest enantioselectivities (Table 1, en-
tries 7 and 8). Interestingly, BPA3 (R1 = H, R2 = Tf) did not promote
the reaction, indicating that a moderately acidic amide proton was
crucial for the allylic amination reaction (Table 1, entries 7–9). Fur-
thermore, chiral phosphine catalyst BPA4 bearing more sterically
hindered groups (R1 = R2 = Ac) did not catalyze the reaction, sug-
gesting that an active amide proton was essential for this reaction
1,10-binaphthyl-20-amine with N-Boc-
D-proline by the same reac-
tion procedure (Scheme 1).
Initial examinations were aimed at determining the most effec-
tive chiral phosphine catalyst for the allylic amination reaction by
performing the reactions of MVK-derived MBH acetate 1a with
phthalimide 2 in tetrahydrofuran (THF) at 10 °C in the presence
of chiral phosphine catalysts (20 mol %). The results of these exper-
iments are summarized in Table 1. Using monophosphine MOP1
(R = H) and MOP2 (R = OMe) as catalysts resulted in the corre-
sponding amination product 3a in good yields and in high regio-
specificities as well as in 10% ee and 36% ee (opposite chiral
induction), respectively (Table 1, entries 1 and 2). Under identical
conditions, chiral phosphine catalyst BP1, which is one of the most
effective catalysts for aza-MBH reactions,11a,b exhibited lower cat-
alytic activity (Table 1, entry 3). Recently, our group designed and
synthesized a series of novel chiral bifunctional phosphine cata-
lysts bearing one phenyl group and an electron-donating alkyl
group [BP2 (R1 = Ph, R2 = Et) and BP3 (R1 = Ph, R2 = nBu)] on the
phosphorus atom.11c,d These more nucleophilic catalysts showed
higher catalytic activities, but the enantioselectivities achieved
were rather low, giving the desired products in almost quantitative
yields within 12 h along with 12–28% ee’s (Table 1, entries 4 and
5). The chiral phosphine catalyst BP4 with two cyclohexyl groups
(Table 1, entry 10). L-Proline-derived trifunctional phosphine cata-
lyst (aR,S)-TPA1 gave the best result, furnishing the amination ad-
duct 3a in almost quantitative yield (95%) and 52% ee (Table 1,
entry 11). Furthermore,
D-proline-derived catalyst (aR,R)-TPA2
could also facilitate this amination reaction under identical condi-
tions. However, the reaction proceeded rather slowly, affording ad-
duct 3a in only 40% chemical yield after 72 h at room temperature
along with 55% ee (Table 1, entry 12). These results reveal that the
chirality of the proline moiety has a certain impact on the reaction
outcome, but do not reveal any significant match/mismatch be-
tween the chirality of binaphthol and proline. N-Boc-protected cat-
alyst (aR,S)-N-Boc-TPA1 could also catalyze this reaction similarly,
affording the desired amination adduct 3a in 85% yield and 33% ee,
suggesting that the active amino proton of the proline moiety
might be indispensable in this reaction (Table 1, entry 13).
Based on the above results, (aR,S)-TPA1 was determined to be
the chiral phosphine catalyst of choice. Therefore, the reaction con-
ditions were further optimized based on the examination of the

1088
G.-N. Ma et al. / Tetrahedron: Asymmetry 20 (2009) 1086–1092
Table 1
Optimization of the catalysts in the asymmetric allylic amination of MBH acetatesa
O
O
OAc O
N
O
Chiral phoshine (20 mol%)
+
∗
º
O
O
THF, 10 C
N
H
O2N
O2N
1a
2
3a
Entry
Chiral phosphine
Time (h)
Yieldb (%)
eec (%)
1
2
3
4
5
6
7
8
9
10
11
12
13
MOP1
MOP2
BP1
BP2
BP3
BP4
BPA1
BPA2
BPA3
BPA4
(aR,S)-TPA1
(aR,R)-TPA2
(aR,S)-N-Boc-TPA1
48
48
48
12
10
72
36
72
72
72
36
72
48
50d
84
65
86
95
30
84
65
n.r.e
n.r.
95
40
10
ꢀ36
14
12
28
13
37
13
n.d.e
n.d.
52
55
33
85
a
Molecular ratio: 1a/2/chiral phosphine = 100/150/20. Reactions were run in THF (0.2 M) at 10 °C.
Isolated yield.
Determined by chiral HPLC (Daicel AD-H column, hexane/isopropanol = 75/25 (v/v), 254 nm, 0.7 mL/min).
The reaction was run at 50 °C.
n.r. = no reaction, n.d. = not determined.
b
c
d
e
solvent effects and the reaction temperatures using (aR,S)-TPA1 as
ee value of 3a diminished slightly, but the reaction time should be
prolonged (Table 2, entry 8). Finally, we found that the optimal
reaction condition for this reaction is using 20 mol % of (aR,S)-
TPA1 as the catalyst in THF (0.2 M) to perform the reaction at 5 °C.
To investigate the scope and limitations of this catalytic asym-
metric allylic amination reaction of MBH acetates, we subse-
quently examined a variety of MBH acetates 1 derived from the
MVK and ethyl vinyl ketone (EVK) under the optimized conditions.
The results are given in Table 3. The corresponding amination ad-
ducts 3 were produced smoothly in good yields (70–91%) and in
modest to good enantioselectivities (34–78% ee’s), whether they
had electron-donating or electron-withdrawing substituents on
the benzene rings (Table 3, entries 1–12). The substrates with
strong electron-withdrawing substituents: 1c (R1 = m-NO2), 1i
(R1 = p-CF3) and 1j (R1 = p-CN) exhibited better results under iden-
tical conditions (Table 3, entries 2, 8, and 9). The o-substituent-
containing substrate 1f produced the corresponding product 3f in
the highest enantioselectivity (up to 78% ee) (Table 3, entry 5).
the catalyst. The results are outlined in Table 2. It was found that
THF is the best solvent in terms of yield and ee of 3a and in toluene,
acetonitrile or ether, compound 3a was obtained in 62–71% yields
and 25–50% ee’s under identical conditions (Table 1, entry 11, and
Table 2, entries 1, 2, and 4). Examination of the reaction tempera-
ture revealed that although no significant decrease in reactivity or
enantioselectivity was observed when the reaction was carried out
in THF at 50 °C or 5 °C, the ee value decreased remarkably in ace-
tonitrile (Table 2, entries 2 and 3, entries 6 and 7). Increasing the
catalyst loading to 30 mol % produced the product in quantitative
yield and in higher enantioselectivity (up to 60% ee) (Table 2, entry
5). When the catalyst loading was reduced to 5 mol %, the yield and
Table 2
Optimization of the reaction conditions of (aR,S)-TPA1-catalyzed allylic amination of
MBH acetatesa
Entry
Catalyst loading
(X mol %)
Solvent Time (h) Temp (°C) Yieldb (%) eec (%)
3. Conclusion
1
2
3
4
5
6
7
8
20
20
20
20
30
20
20
5
Toluene
CH3CN
CH3CN
Et2O
THF
THF
36
48
24
48
24
48
24
96
10
10
50
10
10
5
68
62
71
35
95
90
95
50
25
50
40
28
60
53
50
42
In conclusion, we have developed a multi-functional phos-
phine-catalyzed regio- and enantioselective nucleophilic allylic
amination reaction of MBH acetates prepared from MVK and EVK
using phthalimide as the pronucleophile. The trifunctional phos-
THF
THF
50
50
phine-amide catalyst (aR,S)-TPA1 derived from L-proline gave the
best results in the organophosphine-catalyzed allylic amination
reaction of this category of MBH acetates. In general, the substitu-
tion reaction proceeded smoothly to afford the tandem SN20/SN20
reaction adducts in good yields (70–95%), high regioselectivities,
and medium enantioselectivities (34–78% ee’s). As far as we know,
a
Molecular ratio: 1a/2/(aR,S)-TPA1 = 100/150/X. Reactions were run in solvent
(0.2 M).
b
c
Isolated yield.
Determined by chiral HPLC (Daicel AD-H column, hexane/isopropanol = 75/25
(v/v), 254 nm, 0.7 mL/min).

G.-N. Ma et al. / Tetrahedron: Asymmetry 20 (2009) 1086–1092
1089
Table 3
Asymmetric allylic amination of various MBH acetates 1 with 2a
O
O
OAc O
(aR,S)-TPA1 (20 mol%)
N
*
O
R2
+
º
R2
THF, 5 C, 24-144 h
O
O
N
H
R1
3
1
R1
2
Entry
R1
R2
Time (h)
Yieldb (%)
eec (%)
1
2
3
4
5
6
7
8
9
1b, H
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Et
72
24
72
72
72
3b, 75
3c, 79
3d, 80
3e, 75
3f, 85
3g, 75
3h, 78
3i, 90
3j, 91
3k, 75
3l, 70
3m, 77
34
50
36
44
78
37
36
50
58
45
43
54
1c, m-NO2
1d, p-Cl
1e, m-Cl
1f, o-Cl
1g, p-Br
1h, p-F
1i, p-CF3
1j, p-CN
1k, p-Me
1l, m-Me
1m, p-NO2
72
48
144d
36
10
11
12
72
72
24
a
Molecular ratio: 1/2/(aR,S)-TPA1 = 100/150/20. Reactions were run in THF (0.2 M) at 5 °C.
Isolated yield.
Determined by chiral HPLC.
Reaction was run at ꢀ4 °C and 30 mol % (aR,S)-TPA1 was used.
b
c
d
this work is one of the best results in the phosphine-catalyzed
4.2. General procedure for the synthesis of chiral trifunctional
phosphine amide TPA1
allylic amination of MVK/EVK-derived MBH acetates. Further
application of TPA in asymmetric catalysis is currently in progress
in our group.
N-Boc-L-proline or N-Boc-D-proline (323 mg, 1.5 mmol), DCC
(309 mg, 1.5 mmol), and DMAP (12.7 mg, 0.1 mmol) were
dissolved in CH2Cl2 (10 mL) and the solution was cooled to 0 °C
with an ice-water bath and was stirred for 30 min. A solution of
(R)-(ꢀ)-2-(diphenylphoshino)-1,10-binaphthyl-20-amine (453 mg,
1.0 mmol) in CH2Cl2 (10 mL) was added dropwise over 30 min.
When the addition was completed, the reaction mixture was
warmed to room temperature and stirred for a further 72 h under
an argon atmosphere. Dicyclohexylurea was filtered off and the
solvent was removed under reduced pressure. Then, H2O (5 mL)
was added and the product was extracted with EtOAc
(3 ꢁ 10 mL). The combined organic layers were washed consecu-
tively with 1.0 M KHSO4 (1 ꢁ 25 mL), H2O (1 ꢁ 25 mL), 10% NaH-
CO3 (1 ꢁ 25 mL), and H2O (1 ꢁ 25 mL) and dried over anhydrous
Na2SO4. The solvent was evaporated and the residue was used in
the next step without further purification (This residue was puri-
fied by flash chromatography on silica gel, to give the catalyst
(aR,S)-N-Boc-TPA1 The above residue was dissolved in a mixed
solution of TFA–CH2Cl2 (1/4, v/v, 8.0 mL), and the resulting mixture
was stirred at room temperature for 5 h. Then, the solution was
basified with aqueous ammonia solution (pH > 8) and was ex-
tracted with CH2Cl2 (3 ꢁ 10 mL) and dried over anhydrous Na2SO4.
The solvent was removed under reduced pressure and the residue
was purified by flash chromatography on silica gel (eluent: EtOAc/
MeOH = 5/1), affording (aR,S)-TPA1 or (aR,R)-TPA1 as a snow-
white solid in 65% or 60% overall yield, respectively.
4. Experimental
4.1. General remark
All reactions and manipulations were performed using standard
Schlenk techniques. Melting points were measured on a Yanagim-
oto micro melting apparatus and are uncorrected. NMR spectra
were recorded with a Varian Mercury vx (300 MHz) or Bruker spec-
trometer (400 MHz) (1H NMR), at 75 MHz or 100 MHz (13C NMR) in
CDCl3, respectively. Chemical shifts were reported in ppm down-
field from internal TMS. 31P NMR spectra were recorded at
121 MHz in CDCl3 with 85% H3PO4 as the external reference. J-val-
ues were reported in hertz. Optical rotations were determined at
589 nm (sodium D line) using a Perkin–Elmer 341 MC Polarimeter
and [a]
D values are given in units of 10 cm2 degꢀ1 gꢀ1. Mass spectra
were recorded on the HP-5989 instrument by EI/ESI methods.
Infrared spectra were recorded on a Perkin–Elmer PE-983 spec-
trometer with absorption in cmꢀ1. Chiral HPLC was performed by
using a SHIMADZU SPD-10A vp series instrument with chiral col-
umns (Chiralpak AD-H columns, u 4.6 ꢁ 250 mm, Daicel Chemical
Co. Ltd). Organic solvents used were dried by standard methods
when necessary. Commercially obtained reagents were used with-
out further purification. All reactions were monitored by TLC with
Huanghai GF254 silica gel-coated plates. Flash column chromatog-
raphy was carried out by using 300–400 mesh silica gel at in-
creased pressure. MBH acetates were prepared using literature
method.9 Racemic amination adducts for chiral HPLC analysis were
prepared from the corresponding MBH acetates (0.2 mmol) with
phthalimide (0.3 mmol) in the presence of PPh3 (20–50 mol %) in
THF at room temperature (ca. 5 °C).8a
4.2.1. (2S)-tert-Butyl 2-((R)-20-(diphenylphosphino)-1,10-
binaphthyl-2-ylcarbamoyl)pyrrolidine-1-carboxylate (aR,S)-N-
Boc-TPA1
Yield: 80%; mp 78–80 °C; [
a
]
D = ꢀ22.4 (c 0.91, CHCl3); IR
(CH2Cl2, film) 3383, 3053, 2976, 2879, 1698, 1595, 1501, 1390,
m

1090
G.-N. Ma et al. / Tetrahedron: Asymmetry 20 (2009) 1086–1092
1373, 1161, 1118, 819, 743, 696 cmꢀ1; 1H NMR (400 MHz, CDCl3) d
8.42 (d, J = 8.8 Hz, 1H), 8.01 (d, J = 8.8 Hz, 1H), 7.94 (t, J = 7.6 Hz,
2H), 7.82 (d, J = 8.8 Hz, 1H), 7.57–7.52 (m, 2H), 7.35–7.23 (m,
6H), 7.21–6.90 (m, 9H), 6.79 (d, J = 8.0 Hz, 1H), 3.84 (m, 1H),
3.05–2.91 (m, 1H), 2.47–2.35 (m, 1H), 1.83–1.65 (m, 2H), 1.44–
1.35 (m, 2H), 1.19 (s, 9H); 31P NMR (121 Hz, CDCl3, 85% H3PO4) d
ꢀ12.8; ESI-MS m/z 651.3 (M++1); HRMS (ESI) calcd for
C42H40N2O3P (M++1): 651.2777, found: 651.2769.
4.3.2. N-[2-Acetyl-1-(phenyl)allyl]-phthalimide 3b8a
Yield: 75%; [
D = +54.3 (c 0.54, CHCl3); 1H NMR (300 MHz,
a]
CDCl3) d 7.80 (dd, J = 3.0 Hz, 5.4 Hz, 2H), 7.68 (dd, J = 3.0 Hz,
5.4 Hz, 2H), 7.43–7.25 (m, 5H), 6.37 (d, J = 1.8 Hz, 1H), 6.35 (d,
J = 1.8 Hz, 1H), 5.70 (d, J = 2.1 Hz, 1H), 2.41 (s, 3H); HPLC condition:
Chiralcel AD-H column, k = 230 nm, eluent: hexane/isopropa-
nol = 75/25, flow rate: 0.7 mL/min, tRmajor = 12.63 min, tRmi-
nor = 8.54 min; ee% = 34%.
4.2.2. (2S)-N-((R)-1-(2-(Diphenylphosphino)naphthalen-1-
yl)naphthalen-2-yl)pyrrolidine-2-carboxamide (aR,S)-TPA1
4.3.3. N-[2-Acetyl-1-(30-nitrophenyl)allyl]-phthalimide 3c
Yield: 79%; [
a]
D = ꢀ1.7 (c 0.55, CHCl3); IR (CH2Cl2, film)
m 3085,
Yield: 65%; mp 109–110 °C; [
(CH2Cl2, film) 3227, 3053, 2967, 2960, 2868, 2866, 1686,
1620, 1595, 1503, 1455, 1430, 1335, 1265, 1166, 1093, 1026,
820, 749, 697 cmꢀ1 1H NMR (400 MHz, CDCl3) d 9.25 (s, 1H),
a]
D = ꢀ11.4 (c 2.18, CHCl3); IR
1773, 1718, 1680, 1607, 1522, 1384, 1347, 1108, 1086, 722 cmꢀ1
;
m
1H NMR (300 MHz, CDCl3) d 8.26 (s, 1H), 8.18 (d, J = 8.4 Hz, 1H),
7.84 (dd, J = 3.0 Hz, 5.4 Hz, 2H), 7.78–7.70 (m, 3H), 7.54 (t,
J = 8.4 Hz, 1H), 6.54 (s, 1H), 6.46 (s, 1H), 5.80 (s, 1H), 2.43 (s, 3H);
13C NMR (100 MHz, CDCl3) d 197.7, 167.8, 148.4, 145.1, 139.5,
134.4, 131.5, 129.6, 129.3, 123.6, 123.1, 53. 1, 26.0; EI-MS m/z (rel-
ative intensity %): 350 (23), 307 (100), 291 (97), 261 (65), 104 (78);
HRMS (EI) Anal. Calcd for C19H14N2O5: 350.0903. Found: 350.0905;
HPLC condition: Chiralcel AD-H column, k = 254 nm, eluent: hex-
ane/isopropanol = 85/15, flow rate: 1.0 mL/min, tRmajor = 27.58 min,
tRminor = 33.64 min; ee% = 50%.
;
8.63 (d, J = 8.8 Hz, 1H), 7.99 (d, J = 8.0 Hz, 1H), 7.93–7.88 (m,
2H), 7.81 (d, J = 8.0 Hz, 1H), 7.54 (dd, J = 2.4 Hz, 8.4 Hz, 1H),
7.51–7.44 (m, 1H), 7.30–7.12 (m, 9H), 7.11–7.07 (m, 2H), 7.05–
7.00 (m, 2H), 6.86 (t, J = 8.0 Hz, 1H), 6.73 (d, J = 8.8 Hz, 1H),
3.39 (dd, J = 5.6 Hz, 9.2 Hz, 1H), 2.60–2.52 (m, 1H), 2.29–2.21
(m, 1H), 2.03–1.92 (m, 1H), 1.72–1.65 (m, 2H), 1.49–1.35 (m,
2H); 13C NMR (75 Hz, CDCl3)
d 173.2, 140.9, 140.4, 137.8,
137.6, 137.3, 137.1, 136.5, 136.3, 134.1, 133.9, 133.8, 133.6,
133.5, 133.2, 132.6, 132.5, 130.3, 129.9, 129.0, 128.4, 128.3,
128.2, 128.0, 127.93, 127.87, 127.6, 127.0, 126.9, 126.1, 125.8,
125.7, 124.4, 124.3, 124.2, 119.9, 60.8, 46.6, 30.4, 26.0; 31P
NMR (121 Hz, CDCl3, 85% H3PO4) d ꢀ13.0; ESI-MS m/z 551.2
(M++1); HRMS (ESI) calcd for C37H32N2OP (M++1): 551.2252,
found: 551.2248.
4.3.4. N-[2-Acetyl-1-(40-chlorophenyl)allyl]-phthalimide 3d
Yield: 80%; [
2924, 2854, 1774, 1719, 1686, 1491, 1384, 1356, 1119, 1015,
721 cmꢀ1 1H NMR (400 MHz, CDCl3)
7.81 (dd, J = 2.8 Hz,
a]D = +43.7 (c 0.71, CHCl3); IR (CH2Cl2, film) m 3058,
;
d
5.6 Hz, 2H), 7.70 (dd, J = 2.8 Hz, 5.6 Hz, 2H), 7.35–7.25 (m, 4H),
6.36 (s, 2H), 5.72 (s, 1H), 2.40 (s, 3H); 13C NMR (100 MHz, CDCl3)
d 198.1, 167.9, 145.9, 136.0, 134.1, 134.0, 132.6, 131.7, 130.1,
128.9, 123.4, 53.4, 26.1; EI-MS m/z (relative intensity %): 339 (9),
296 (100), 262 (38), 192 (15), 149 (13); HRMS (EI) Anal. Calcd for
C19H14NO3Cl: 339.0662. Found: 339.0665; HPLC condition: Chiral-
cel AD-H column, k = 230 nm, eluent: hexane/isopropanol = 80/20,
flow rate: 0.5 mL/min, tRmajor = 34.02 min, tRminor = 29.01 min;
ee% = 36%.
4.2.3. (2R)-N-((R)-1-(2-(Diphenylphosphino)naphthalen-1-
yl)naphthalen-2-yl)pyrrolidine-2-carboxamide (aR,R)-TPA2
Yield: 60%; mp 84–85 °C; [
(CH2Cl2, film) 3390, 3053, 2927, 2868, 1767, 1688, 1503,
1410, 1215, 1166, 910, 744, 697 cmꢀ1 1H NMR (400 MHz,
CDCl3) 9.31 (s, 1H), 8.66 (d, J = 8.8 Hz, 1H), 8.01 (d,
a]D = +20.1 (c 0.53, CHCl3); IR
m
;
d
J = 8.0 Hz, 1H), 7.91 (d, J = 8.4 Hz, 1H), 7.88 (d, J = 8.0 Hz, 2H),
7.56 (dd, J = 2.0 Hz, 8.4 Hz, 1H), 7.47 (t, J = 7.6 Hz, 1H), 7.34–
7.08 (m, 14H), 7.00 (d, J = 8.4 Hz, 1H), 3.32 (dd, J = 3.6 Hz,
9.6 Hz, 1H), 2.28–2.22 (m, 1H), 1.71–1.67 (m, 1H), 1.34–1.26
(m, 2H), 1.17–1.12 (m, 1H), 0.89–0.84 (m, 1H), 0.63–0.52 (m,
1H); 31P NMR (121 Hz, CDCl3, 85% H3PO4) d ꢀ14.4; ESI-MS m/
4.3.5. N-[2-Acetyl-1-(30-chlorophenyl)allyl]-phthalimide 3e
Yield: 75%; [
3058, 2925, 2854, 1773, 1715, 1681, 1468, 1385, 1364, 1113,
1082, 723 cmꢀ1 1H NMR (400 MHz, CDCl3) d 7.82 (dd, J = 2.8 Hz,
a]D = +127.4 (c 0.85, CHCl3); IR (CH2Cl2, film) m
;
5.6 Hz, 2H), 7.71 (dd, J = 2.8 Hz, 5.6 Hz, 2H), 7.39 (s, 1H), 7.37–
7.27 (m, 3H), 6.39 (s, 1H), 6.36 (s, 1H), 5.74 (d, J = 0.8 Hz, 1H),
2.41 (s, 3H); 13C NMR (100 MHz, CDCl3) d 198.0, 167.9, 145.7,
139.5, 134.5, 134.1, 131.7, 129.9, 129.2, 128.7, 128.3, 126.8,
123.4, 53.4, 26.0; EI-MS m/z (relative intensity %): 339 (10), 296
(100), 262 (28), 192 (8), 149 (14); HRMS (EI) Anal. Calcd for
C19H14NO3Cl: 339.0662. Found: 339.0663; HPLC condition: Chiral-
cel AD-H column, k = 230 nm, eluent: hexane/isopropanol = 80/20,
flow rate: 0.7 mL/min, tRmajor = 19.21 min, tRminor = 17.02 min;
ee% = 44%.
z
551.2 (M++1); HRMS (ESI) calcd for C37H32N2OP (M++1):
551.2252, found: 551.2246.
4.3. General procedure for the asymmetric allylic amination of
MBH acetates
To a flame-dried Schlenk tube charged with the corresponding
MBH acetates 1 (0.2 mmol), phthalimide 2 (0.3 mmol, 44.1 mg),
and (aR,S)-TPA1 (0.04 mmol, 22.0 mg) was added anhydrous THF
(1.0 mL). The reaction mixture was allowed to stir at room temper-
ature (ca. 5 °C) under an argon atmosphere. The reaction was mon-
itored by TLC plate analysis. After the starting substrates were
consumed, the solvent was removed under reduced pressure and
the residue was purified by a silica gel column chromatography
(eluent: EtOAc/petroleum ether = 1/6 to 1/4) to give the corre-
sponding amination adducts 3.
4.3.6. N-[2-Acetyl-1-(20-chlorophenyl)allyl]-phthalimide 3f
Yield: 85%; [
2925, 2854, 1774, 1715, 1681, 1468, 1387, 1365, 1109, 1039,
723 cmꢀ1 1H NMR (400 MHz, CDCl3)
7.82 (dd, J = 2.8 Hz,
a]D = +49.3 (c 0.5, CHCl3); IR (CH2Cl2, film) m 3065,
;
d
5.2 Hz, 2H), 7.71 (dd, J = 2.8 Hz, 5.2 Hz, 2H), 7.42–7.35 (m, 2H),
7.27–7.22 (m, 2H), 6.78 (s, 1H), 6.38 (s, 1H), 5.69 (s, 1H), 2.42 (s,
3H); 13C NMR (100 MHz, CDCl3) d 197.7, 167.9, 144.5, 134.9,
134.3, 134.1, 133.6, 132.6, 131.7, 129.8, 129.3, 128.7, 126.9,
123.6, 123.4, 51.4, 26.0; EI-MS m/z (relative intensity %): 339 (3),
304 (100), 296 (7), 157 (7), 149 (6); HRMS (EI) Anal. Calcd for
C19H14NO3Cl: 339.0662. Found: 339.0665; HPLC condition: Chiral-
cel AD-H column, k = 230 nm, eluent: hexane/isopropanol = 80/20,
flow rate: 0.7 mL/min, tRmajor = 18.71 min, tRminor = 14.97 min;
ee% = 78%.
4.3.1. N-[2-Acetyl-1-(40-nitrophenyl)allyl]-phthalimide 3a8a
Yield: 99%; 1H NMR (300 MHz, CDCl3) d 8.21 (d, J = 9.0 Hz, 2H),
7.83 (dd, J = 3.0 Hz, 5.4 Hz, 2H), 7.74 (dd, J = 3.0 Hz, 5.4 Hz, 2H),
7.56 (d, J = 9.0 Hz, 2H), 6.53 (s, 1H), 6.44 (s, 1H), 5.76 (s, 1H), 2.43
(s, 3H); HPLC condition: Chiralcel AD-H column, k = 254 nm, elu-
ent: hexane/isopropanol = 75/25, flow rate: 0.7 mL/min, tRma-
jor = 29.28 min, tRminor = 31.12 min; ee% = 52%.

G.-N. Ma et al. / Tetrahedron: Asymmetry 20 (2009) 1086–1092
1091
4.3.7. N-[2-Acetyl-1-(40-bromophenyl)allyl]-phthalimide 3g
Yield: 75%; [ D = +73.0 (c 0.1, CHCl3); IR (CH2Cl2, film) 3060,
2925, 2854, 1771, 1714, 1681, 1488, 1384, 1363, 1114, 1012,
721 cmꢀ1 1H NMR (400 MHz, CDCl3)
7.80 (dd, J = 3.2 Hz,
4.8 Hz, 2H), 7.70 (dd, J = 3.2 Hz, 4.8 Hz, 2H), 7.47 (d, J = 8.0 Hz,
2H), 7.28 (d, J = 8.0 Hz, 2H), 6.37 (s, 1H), 6.35 (s, 1H), 5.72 (s, 1H),
2.40 (s, 3H); 13C NMR (100 MHz, CDCl3) d 198.0, 167.9, 145.8,
136.5, 134.1, 131.8, 131.6, 130.3, 128.9, 123.3, 122.1, 53.4, 26.0;
EI-MS m/z (relative intensity %): 383 (9), 340 (70), 262 (100), 193
(16), 130 (49); HRMS (EI) Anal. Calcd for C19H14NO3Br: 383.0157.
Found: 383.0158; HPLC condition: Chiralcel AD-H column,
k = 230 nm, eluent: hexane/isopropanol = 80/20, flow rate:
0.7 mL/min, tRmajor = 25.13 min, tRminor = 21.53 min; ee% = 37%.
J = 8.0 Hz, 2H), 6.34 (s, 1H), 6.33 (s, 1H), 5.72 (d, J = 1.6 Hz, 1H), 2.39
(s, 3H), 2.32 (s, 3H); 13C NMR (100 MHz, CDCl3) d 198.4, 168.1,
146.5, 137.8, 134.5, 133.9, 131.9, 129.4, 128.7, 128.5, 123.3, 53.8,
26.2, 21.1; EI-MS m/z (relative intensity %): 319 (11), 304 (27),
276 (100), 172 (63), 129 (22); HRMS (EI) Anal. Calcd for
C20H17NO3: 319.1208. Found: 319.1210; HPLC condition: Chiralcel
AD-H column, k = 230 nm, eluent: hexane/isopropanol = 80/20,
flow rate: 0.7 mL/min, tRmajor = 22.04 min, tRminor = 18.54 min;
ee% = 45%.
a
]
m
;
d
4.3.12. N-[2-Acetyl-1-(30-methylphenyl)allyl]-phthalimide 3l
Yield: 70%; [
2926, 2856, 1773, 1736, 1718, 1697, 1677, 1491, 1385, 1351,
1000, 719 cmꢀ1 1H NMR (400 MHz, CDCl3) d 7.81 (dd, J = 3.2 Hz,
a]D = +153.0 (c 0.49, CHCl3); IR (CH2Cl2, film) m
;
4.3.8. N-[2-Acetyl-1-(40-fluorophenyl)allyl]-phthalimide 3h
5.6 Hz, 2H), 7.69 (dd, J = 3.2 Hz, 5.6 Hz, 2H), 7.21 (dd, J = 7.2 Hz,
13.6 Hz, 2H), 7.19 (s, 1H) 7.12 (d, J = 7.2 Hz, 2H), 6.34 (s, 1H),
6.32 (s, 1H), 5.70 (d, J = 1.2 Hz, 1H), 2.40 (s, 3H), 2.33 (s, 3H); 13C
NMR (100 MHz, CDCl3) d 198.3, 168.1, 146.5, 138.4, 137.4, 133.9,
131.8, 129.2, 128.9, 128.8, 128.5, 125.6, 123.3, 54.0, 26.1, 21.4;
EI-MS m/z (relative intensity %): 319 (18), 304 (24), 276 (100),
172 (37), 129 (23); HRMS (EI) Anal. Calcd for C20H17NO3:
319.1208. Found: 319.1207; HPLC condition: Chiralcel AD-H col-
umn, k = 230 nm, eluent: hexane/isopropanol = 80/20, flow rate:
0.5 mL/min, tRmajor = 27.71 min, tRminor = 19.54 min; ee% = 43%.
Yield: 78%; [
2925, 2854, 1771, 1714, 1606, 1468, 1385, 1363, 1113, 1088,
719 cmꢀ1 1H NMR (400 MHz, CDCl3)
7.81 (dd, J = 2.8 Hz,
a]D = +47.4 (c 0.31, CHCl3); IR (CH2Cl2, film) m 3058,
;
d
5.6 Hz, 2H), 7.70 (dd, J = 2.8 Hz, 5.6 Hz, 2H), 7.39 (dd, J =1.2 Hz,
8.8 Hz, 2H), 7.03 (t, J = 8.8 Hz, 2H), 6.37 (s, 1H), 6.35 (s, 1H), 5.71
(d, J = 1.6 Hz, 1H), 2.40 (s, 3H); 13C NMR (100 MHz, CDCl3) d
1
198.2, 168.0, 162.4 (d, JC–F = 245.6 Hz), 146.3, 134.1, 133.3 (d,
3
4JC–F = 3.3 Hz), 131.7, 130.5 (d, JC–F = 8.2 Hz); 128.7, 123.4, 115.6
2
(d, JC–F = 21.4 Hz), 53.4, 26.1; EI-MS m/z (relative intensity %):
323 (8), 281 (16), 280 (100), 176 (26), 133 (19); HRMS (EI) Anal.
Calcd for C19H14NO3F: 323.0958. Found: 323.0960; HPLC condi-
tion: Chiralcel AD-H column, k = 230 nm, eluent: hexane/isopropa-
4.3.13. N-[2-Propyl-1-(40-nitrophenyl)allyl]-phthalimide 3m
Yield: 77%; [
1773, 1735, 1718, 1697, 1608, 1521, 1385, 1351, 1107, 1086,
719 cmꢀ1 1H NMR (400 MHz, CDCl3) d 8.21 (d, J = 8.8 Hz, 2H)
a]D = +27.5 (c 1.01, CHCl3); IR (CH2Cl2, film) m 3082,
nol = 80/20,
flow
rate:
0.7 mL/min,
tRmajor = 23.42 min,
tRminor = 19.01 min; ee% = 36%.
;
7.84 (dd, J = 2.8 Hz, 5.6 Hz, 2H), 7.74 (dd, J = 2.8 Hz, 5.6 Hz, 2H),
7.56 (d, J = 8.8 Hz, 2H), 6.55 (s, 1H), 6.43 (s, 1H), 5.72 (d,
J = 0.8 Hz, 1H), 2.79–2.85 (m, 2H), 1.08 (t, J = 7.2 Hz, 3H); 13C
NMR (100 MHz, CDCl3) d 200.4, 167.8, 147.6, 144.7, 144.6, 134.4,
131.6, 129.6, 128.1, 123.9, 123.6, 53.4, 31.0, 8.1; EI-MS m/z (relative
intensity %): 364 (8), 335 (44), 307 (100), 291 (20), 104 (47); HRMS
(EI) Anal. Calcd for C20H16N2O5: 364.1059. Found: 364.1060; HPLC
condition: Chiralcel AD-H column, k = 254 nm, eluent: hexane/iso-
propanol = 80/20, flow rate: 0.5 mL/min, tRmajor = 64.35 min,
tRminor = 60.56 min; ee% = 54%.
4.3.9. N-[2-Acetyl-1-(40-trifluoromethylphenyl)allyl]-
phthalimide 3i
Yield: 90%; [a]D = +79.0 (c 0.5, CHCl3); IR (CH2Cl2, film) m 2926,
1774, 1716, 1682, 1468, 1386, 1325, 1167, 1125, 1068, 719 cmꢀ1
;
1H NMR (400 MHz, CDCl3) d 7.83 (dd, J = 3.2 Hz, 5.6 Hz, 2H), 7.72
(dd, J = 3.2 Hz, 5.6 Hz, 2H), 7.61 (d, J = 8.0 Hz, 2H), 7.53 (d,
J = 8.0 Hz, 2H), 6.47 (s, 1H), 6.41 (s, 1H), 5.73 (d, J = 1.2 Hz, 1H),
2.42 (s, 3H); 13C NMR (100 MHz, CDCl3) d 197.9, 167.9, 145.5,
2
141.4, 134.2, 131.6, 130.2 (q, JC–F = 32.6 Hz), 129.2, 129.0, 125.6
3
1
(q, JC–F = 3.6 Hz), 123.9 (q, JC–F = 270.6 Hz), 123.4, 53.4, 26.0; EI-
MS m/z (relative intensity %): 373 (6), 330 (100), 304 (14), 183
(12), 104 (6); HRMS (EI) Anal. Calcd for C20H14NO3F3: 373.0926.
Found: 373.0929; HPLC condition: Chiralcel AD-H column,
k = 230 nm, eluent: hexane/isopropanol = 90/10, flow rate:
1.0 mL/min, tRmajor = 20.11 min, tRminor = 18.68 min; ee% = 50%.
Acknowledgments
The Shanghai Municipal Committee of Science and Technology
(06XD14005, 08dj1400100-2), the National Basic Research Pro-
gram of China (973)-2009CB825300, and the National Natural Sci-
ence Foundation of China (20472096, 20872162, 20672127,
20821002, and 20732008) are acknowledged for the financial
support.
4.3.10. N-[2-Acetyl-1-(40-cyanophenyl)allyl]-phthalimide 3j
Yield: 91%; [
2924, 2854, 2229 (C„N), 1773, 1719, 1610, 1467, 1384, 1364,
1103, 1068, 717 cmꢀ1 1H NMR (400 MHz, CDCl3) d 7.83 (dd,
a]D = +49.7 (c 0.49, CHCl3); IR (CH2Cl2, film) m 3068,
;
References
J = 3.2 Hz, 5.2 Hz, 2H), 7.73 (dd, J = 3.2 Hz, 5.2 Hz, 2H), 7.65 (d,
J = 8.0 Hz, 2H), 7.51 (d, J = 8.0 Hz, 2H), 6.47 (s, 1H), 6.42 (s, 1H),
5.74 (s, 1H), 2.42 (s, 3H); 13C NMR (100 MHz, CDCl3) d 197.8,
167.7, 145.1, 142.6, 134.3, 132.4, 131.5, 129.32, 129.28, 123.5,
118.4, 112.0, 52.3, 26.0; EI-MS m/z (relative intensity %): 331 (7),
288 (17), 287 (100), 140 (11), 104 (7); HRMS (EI) Anal. Calcd for
C20H14N2O3: 330.1004. Found: 330.0996; HPLC condition: Chiralcel
AD-H column, k = 230 nm, eluent: hexane/isopropanol = 80/20,
flow rate: 0.7 mL/min, tRmajor = 38.64 min, tRminor = 54.75 min;
ee% = 58%.
1. (a) Morita, K.; Suzuki, Z.; Hirose, H. Bull. Chem. Soc. Jpn. 1968, 41, 2815; (b)
Baylis, A. B.; Hillman, M. E. D. German Patent 2155113, 1972; Chem. Abstr.
1972, 77, 34174q.
2. For selected reviews on the Morita–Baylis–Hillman reaction, see: (a) Drewes, S.
E.; Roos, G. H. P. Tetrahedron 1988, 44, 4653–4670; (b) Basavaiah, D.; Rao, P. D.;
Hyma, R. S. Tetrahedron 1996, 52, 8001–8062; (c) Ciganek, E.. In Org. React;
Paquette, L. A., Ed.; Wiley: New York, 1997; Vol. 51, pp 201–350; (d) Langer, P.
Angew. Chem., Int. Ed. 2000, 39, 3049–3051; (e) Basavaiah, D.; Rao, A. J.;
Satyanarayana, T. Chem. Rev. 2003, 103, 811–892; (f) Masson, G.; Housseman,
C.; Zhu, J. Angew. Chem., Int. Ed. 2007, 46, 4614–4628; (g) Basavaiah, D.; Rao, K.
V.; Reddy, R. J. Chem. Soc. Rev. 2007, 36, 1581–1588; (h) Menozzi, C.; Dalko, P. I.
Organocatalytic Enantioselecttive Morita–Baylis–Hillman Reactions. In
Enantioselective Organocatalysis; Dalko, P. I., Ed.; Reactions and Experimental
Procedures; Wiley-VCH: Weinheim, 2007; (i) Dederck, V.; Mattinez, J.; Lamaty,
F. Chem. Rev. 2009, 109, 1–48.
4.3.11. N-[2-Acetyl-1-(40-methylphenyl)allyl]-phthalimide 3k
Yield: 75%; [
2853, 1773, 1736, 1712, 1686, 1677, 1467, 1384, 1351, 1105, 1019,
716 cmꢀ1 1H NMR (400 MHz, CDCl3) d 7.80 (dd, J = 3.2 Hz, 5.6 Hz,
2H), 7.68 (dd, J = 3.2 Hz, 5.6 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 7.15 (d,
a]D = +55.0 (c 0.30, CHCl3); IR (CH2Cl2, film) m 2924,
3. For recent reports on the utilization of MBH adducts reactions, see: (a)
Aggarwal, V. K.; Patin, A.; Tisserand, S. Org. Lett. 2005, 7, 2555–2557; (b)
Kabalka, G. W.; Venkataiah, B.; Dong, G. Organometallics 2005, 24, 762–764; (c)
Du, Y.; Feng, J.; Lu, X. Org. Lett. 2005, 7, 1987–1989; (d) Shafiq, Z.; Liu, L.; Liu, Z.;
;

1092
G.-N. Ma et al. / Tetrahedron: Asymmetry 20 (2009) 1086–1092
Wang, D.; Chen, Y.-J. Org. Lett. 2007, 9, 2525–2528; (e) Dlaigh, C.; Connon, S. J. J.
7. (a) Basavaiah, D.; Kumaragurubaran, N.; Sharada, D. S.; Reddy, R. M.
Tetrahedron 2001, 57, 8167–8172; (b) Du, Y.-S.; Han, X.-L.; Lu, X.-Y.
Tetrahedron Lett. 2004, 45, 4967–4971; (c) van Steenis, D. J. V. C.; Marcelli, T.;
Lutz, M.; Spek, A. L.; van Maarseveen, J. H.; Hiemstra, H. Adv. Synth. Catal. 2007,
349, 281–286.
8. (a) Cho, C.-W.; Kong, J.-R.; Krische, M. J. Org. Lett. 2004, 6, 1337–1339; (b) Cho,
C-W.; Krische, M. J. Angew. Chem. Int. Ed. 2004, 43, 6689–6691; (c) Park, H.; Cho,
O. W.; Krische, M. J. J. Org. Chem. 2006, 71, 7892–7894.
9. Zhang, T.-Z.; Dai, L.-X.; Hou, X.-L. Tetrahedron: Asymmetry 2007, 18, 1990–1994.
10. (a) Uozumi, Y.; Hayashi, T. J. Am. Chem. Soc. 1991, 113, 9887–9888; (b) Uozumi,
Y.; Tamahashi, A.; Lee, S. Y.; Hayashi, T. J. Org. Chem. 1993, 58, 1945–1948.
11. (a) Shi, M.; Chen, L.-H. Chem. Commum. 2003, 1310–1311; (b) Shi, M.; Chen, L.-
H.; Li, C.-Q. J. Am. Chem. Soc. 2005, 127, 3790–3800; (c) Lei, Z.-Y.; Ma, G.-N.; Shi,
M. Eur. J. Org. Chem. 2008, 3817–3820; (d) Lei, Z.-Y.; Liu, X.-G.; Shi, M.; Zhao,
M.-X. Tetrahedron: Asymmetry 2008, 19, 2058–2062.
12. (a) Sumi, K.; Ikariya, T.; Noyori, R. Can. J. Chem. 2000, 78, 697–703; (b) Botman,
P. N. M.; David, O.; Amore, A.; Dinkelaar, J.; Vlaar, M. T.; Goubitz, K.; Fraanje, J.;
Schenk, H.; Hiemsta, H.; van Maarseveen, J. H. Angew, Chem., Int. Ed. 2004, 43,
3471–3473; (c) Qi, M.-J.; Ai, T.; Shi, M.; Li, G. Tetrahedron 2008, 64, 1181–1186.
Org. Chem. 2007, 72, 7066–7069; (f) Kantam Lakshmi, M.; Shiva Kumar, K. B.;
Sreedhar, B. J. Org. Chem. 2008, 73, 320–322; (g) Jiang, Y.-Q.; Shi, Y.-L.; Shi, M. J.
Am. Chem. Soc. 2008, 130, 7202–7203.
4. The enantioselective Pd-catalyzed allylic alkylation of MBH acetates has been
reported, see: (a) Trost, B. M.; Tsui, H.-C.; Toste, F. D. J. Am. Chem. Soc. 2000, 122,
3534–3535; (b) Trost, B. M.; Thiel, O. R.; Tsui, H.-C. J. Am. Chem. Soc. 2002, 124,
11616–11617; (c) Thiel, O. R.; Trost, B. M.; Tsui, H.-C. J. Am. Chem. Soc. 2003,
125, 13155–13164; (d) Trost, B. M.; Machacek, M. R.; Tsui; H, -C. J. Am. Chem.
Soc. 2005, 127, 7014–7024; (e) Trost, B. M.; Brennan, M. K. Org. Lett. 2007, 9,
3961–3964; For Pd-catalyzed allylic amination of MBH acetates, see: (f)
Nemoto, T.; Fukuyama, T.; Yamamoto, E.; Tamura, S.; Fukuda, T.; Matsumto, T.;
Akimoto, Y.; Hamada, Y. Org. Lett. 2007, 9, 927–930.
5. (a) Kim, J. N.; Lee, H. J.; Lee, K. Y.; Gong, J. H. Synlett 2002, 173–175; (b)
Gong, J. H.; Kim, H. R.; Ryu, E. K.; Kim, J. N. Bull. Korean Chem. Soc. 2002,
23, 789–790; (c) Kim, J. N.; Lee, H. J.; Gong, J. H. Tetrahedron Lett. 2002, 43,
9141–9146.
6. Ciclosi, M.; Fava, C.; Galeazzi, R.; Orena, M.; Sepulveda-Arques, J. Tetrahedron
Lett. 2002, 43, 2199–2202.