An N-linked bidentate phosphoramidite ligand (N-Me-BIPAM) for rhodium-catalyzed asymmetric addition of arylboronic acids to N-sulfonylarylaldimines

Article abstract of DOI:10.1002/adsc.200800631

A chiral N-linked C₂-symmetric bidentate phosphoramidite (N-Me-BIPAM) was newly developed for the rhodium-catalyzed enantioselective addition of arylboronic acids to N-sulfonylimines. This ligand achieved high enantioselectivities in a range of

Full text of DOI:10.1002/adsc.200800631

FULL PAPERS
DOI: 10.1002/adsc.200800631
An N-Linked Bidentate Phosphoramidite Ligand
(N-Me-BIPAM) for Rhodium-Catalyzed Asymmetric Addition
of Arylboronic Acids to N-Sulfonylarylaldimines
Kazunori Kurihara,a Yasunori Yamamoto,a,* and Norio Miyauraa,*
a
Division of Chemical Process Engineering, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628,
Japan
Fax : (+81)-11-706-6561; e-mail: yasuyama@eng.hokudai.ac.jp or miyaura@eng.hokudai.ac.jp
Received: October 14, 2008; Published online: December 29, 2008
Abstract: A chiral N-linked C2-symmetric bidentate of 84–99% ee in additions of arylboronic acids to N-
phosphoramidite (N-Me-BIPAM) was newly devel- tosyl- and N-nosylarylaldimines.
oped for the rhodium-catalyzed enantioselective ad-
dition of arylboronic acids to N-sulfonylimines. This Keywords: arylboronic acids; asymmetric catalysis;
ligand achieved high enantioselectivities in a range asymmetric synthesis; diarylamines; N-sulfonylald-
AHCTUNGTRENGNiUN mines
Introduction
paracyclophane-based ketimine catalysts has been re-
ported for analogous arylations of N-sulfonylimines
Chiral diarylmethylamines are an important fragment and N-formylimines with arylstannanes[10] or arylzinc
involved in a variety of pharmacologiocally significant compounds.[9]
compounds.[1] For achieving a simple access to this
In the course of our study on bisphosphoroamidites
versatile skeleton, rhodium-catalyzed enantioselective as a chiral ligand for enantioselective bond-forming
arylations of imines with arylboron,[2–8] -zinc,[9] -stan- reactions,[13] we found a novel N-linked bidentate
nane[10] and -titanium compounds[11] have been devel- phosphoramidite (N-Me-BIPAM) that is effective for
oped. Among these extensive studies on catalytic ad- the arylation of both N-sulfonyl
dition of metallic and non-metallic compounds to al-
dimines, the use of arylboronic acids has attracted
much attention due to their low toxicity, compatibility
to a broad range of functional groups and high stabili-
ty in water and air. The enantioselective rhodium-cat-
alyzed arylation of aldimines with arylboroxines or ar-
ylboronic acids has been studied by Tomioka,[3]
Zhou,[4] de Vries, Feringa and Minnerd,[5] Ellman,[6]
Hayashi,[7] as well as Xu and Lin.[8] Amidophosphane
ACHTUNGTREN(NUNG aryl)imines (9–11)
(1), spiromonophosphite (2), bicycloACHTUNGTREN[NGNU 2.2.2]octadiene
(6), bicyclo[3.3.1]nonadiene (7) and tetrahydropenta-
ACHTUNGTRENNUNG
lene (8) were found to be effective as the chiral
ligand for arylation of N-tosyl- (4-MeC6H4SO2) and
N-nosylimines (4-NO2C6H4SO2) (Figure 1). Phosphor-
amidite (3) was used for N-SO2NMe2 imines,[5] and
deguphos
[bis(diphenylphosphino)-1-benzylpyrroli-
dine] (5) gave high enantioselectivities for N-
P(=O)Ph2 imines and N-Boc imines.[6b] Thus, both
monodentate and bidentate phosphorus ligands have
been used successfully as chiral ligands, although the
traditional BINAP (4) is less efficient in terms of
chemical yields and enantioselectivities. The efficiency
of Rh/chiral monodentate phosphine (MOP) and Figure 1. Chiral ligands reported for the arylation of imines.
260
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An N-Linked Bidentate Phosphoramidite Ligand (N-Me-BIPAM)
FULL PAPERS
complex (RhACHTUNTRGNEUNG(acac)(N-Me-BIPAM) was also con-
firmed by HR-MS (ESI), calcd. for C52H49N3O6P2Rh:
976.2152, found: 976.2148 (M+H).
Reaction Conditions
Scheme 1. Arylation of imines.
Several combinations of rhodium(I) precursors and
solvents for N-Me-BIPAM (19) revealed the high effi-
ciency of RhACTHNUGTRENN(GU acac)HCAUTNGTREN(NNGU C2H4)2 in DME for the addition of
with arylboronic acids (Scheme 1). The reaction pro- PhB(OH)2 to 4-methoxybenzylaldehyde N-tosylimine
vided a-diarylmethylamines (13–15) with high yields (9b) (Table 1). The reaction took place smoothly at
and high enantioselectivities up to 99% ee in the pres- 508C in the presence of 1.5 equivalents of PhB(OH)2
ence of 1.5 equivalents of boronic acids.
with 88% yield and 94% ee (entry 4). Thus, the reac-
tion did not require the use of bases and a large
excess of boronic acids or boroxines to achieve practi-
cal yields. On the other hand, the rhodium(I)-chloro
complex previously used for 1,4-addition of arylbor-
onic acid to a,b-unsaturated carbonyl compounds[13]
unexpectedly did not catalyze the reaction even in the
Results and Discussion
Rhodium Catalyst
We previously reported that an O-linked bidentate presence of a base (entries 6 and 7). It is also interest-
phosphoramidite (18, Me-BIPAM) synthesized on the ing that Me-BIPAM (18),[13] which achieved high
basis of Shibasakiꢁs O-linked BINOL (16)[13] is an ex- enantioselectivities in the 1,4-addition of arylboronic
cellent ligand for rhodium-catalyzed 1,4-addition of acids to cyclic and acyclic enones, resulted in a signifi-
arylboronic acids to a,b-unsaturated carbonyl com- cantly lower enantioselectivity than did N-Me-
pounds. The corresponding N-linked C2-symmetric BIPAM (entry 8). Among the N-tosyl- (9, 4-
phosphoramidite (19, N-Me-BIPAM) was newly syn- MeC6H4SO2), N-nosyl- (10, 4-NO2C6H4SO2), and N-
thesized by treatment of 17[12] with
PACHTUNGTRENNUNG
(Scheme 2).
The 31P NMR spectrum of the mixture of Rh
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
160.0 ppm (d, JRh,P =292.3 Hz), thus suggesting the in-
tramolecular complexation of two phosphorus atoms
to a rhodium metal center. The formation of a 1:1
Table 1. Reaction conditions.[a]
Entry Imine Rh complex
Solvent Yield [%] ee [%]
1
2
3
4
5
6
9b
9b
9b
9b
9b
9b
9b
9b
10a
11a
Rh
Rh(acac)
Rh(acac)
Rh(acac)(C2H4)2 DME
N
ACHTNUGTNER(UNNG C2H4)2 toluene 66 (13bg) 77
A
86 (13bg) 64
ACHTNUGTNER(UNNG C2H4)2 dioxane 70 (13bg) 87
A
88 (13bg) 94
34 (13bg) 88
[Rh
[Rh
[Rh
C
DME
DME
DME
trace
–
7[b]
8[c]
9
trace
–
Rh
Rh(acac)
Rh(acac)(C2H4)2 DME
A
R
83 (13bg) 74
72 (14ag) 93
89 (15ag) 87
A
ACHTUNGTRENNUNG
10
A
ACHTUNGTRENNUNG
[a]
A
mixture of aldimine (0.5 mmol), PhB(OH)2
(0.75 mmol), Rh complex (3 mol%) and N-Me-BIPAM
(3.3 mol%) in solvent (2 mL) was stirred at 508C for
16 h.
In the presence of aqueous KOH (20 mol%).
Me-BIPAM was used instead of N-Me-BIPAM.
[b]
[c]
Scheme 2. Synthesis of N-Me-BIPAM.
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Kazunori Kurihara et al.
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Scope and Limitation
However, this ligand may prefer some steric hin-
drance of substituents since the reaction often result-
Results of the arylation of aromatic imines with aryl- ed in less than 90% ee when an unsubstituted phenyl
boronic acids at 508C in DME in the presence of a group was used for either of the two aryl rings (en-
RhACHTUNGTRENNUNG(acac)ACHTUNGTRENNUNG(C2H4)2/N-Me-BIPAM catalyst (3 mol%) are tries 1, 2, 19, 21 28, 30 and 35). This is due to steric
summarized in Table 2. High enantioselectivities were reasons rather than an electronic effect of substituents
achieved in most combinations of two aromatic rings because high selectivities were easily achieved in all
having donating or withdrawing substituents at the combinations of two aryl rings possessing substituents
para, meta or ortho carbons of imines and boronic in both rings. The presence of an ortho-substituent in
acids. Thus, the performance of N-Me-BIPAM is com- imines did not retard the reaction (entries 20–32), but
parable to or even higher than that of ligands previ- 2-methyl- and 2-methoxyphenylboronic acids resulted
ously reported for analogous arylations of imines.[3–8]
Table 2. Arylation of N-tosylimines (9, Scheme 1).[a]
Entry
Ar1
Ar2
Product
Yield [%]
ee [%]
1
2
3
4
5
6
7
8
C6H5 (9a)
C6H5 (9a)
C6H5 (9a)
C6H5 (9a)
C6H5 (9a)
C6H5 (9a)
4-MeOC6H4 (12a)
4-MeC6H4 (12b)
4-ClC6H4 (12c)
4-CF3C6H4 (12d)
3-F-4-MeOC6H3 (12e)
1-naphthyl (12f)
C6H5 (12g)
4-MeOC6H4 (12a)
C6H5 (12g)
4-MeOC6H4 (12a)
C6H5 (12g)
4-CF3C6H4 (12d)
C6H5 (12g)
C6H5 (12g)
C6H5 (12g)
C6H5 (12g)
C6H5 (12g)
4-MeOC6H4 (12a)
C6H5 (12g)
C6H5 (12g)
C6H5 (12g)
4-CF3C6H4 (12d)
4-CF3C6H4 (12d)
4-MeOC6H4 (12a)
3-MeOC6H4 (12h)
4-CF3C6H4 (12d)
4-MeOC6H4 (12a)
C6H5 (12g)
4-MeOC6H4 (12a)
C6H5 (12g)
4-CF3C6H4 (12d)
C6H5 (12g)
13aa
13ab
13ac
13ad
13ae
13af
13bg
13ca
13cg
13da
13dg
13dd
13eg
13fg
13gg
13hg
13ig
91
96
82
89
96
61
88
92
91
93
98
91
87
91
95
92
98
99
90
93
84
74
70
99
92
99
77
89
99
95
96
98
91
93
89
99
86
95
85 (R)
84 (R)
95 (R)
90 (R)
97
93 (R)
94 (S)
96 (R)
96 (S)
98 (S)
95 (S)
92
94 (S)
96 (S)
99 (S)
97
92
97
85
99
18 (S)
98
93
96 (S)
93
96
96
88
4-MeOC6H4 (9b)
4-MeC6H4 (9c)
4-MeC6H4 (9c)
4-ClC6H4 (9d)
4-ClC6H4 (9d)
4-ClC6H4 (9d)
4-BrC6H4 (9e)
4-CF3C6H4 (9f)
3-MeOC6H4 (9g)
3-ClC6H4 (9h)
3-Br-4-MeOC6H3 (9i)
3,4-(CH2O2)C6H3 (9j)[c]
3,4-(CH2O2)C6H3 (9j)[c]
2,3-(C2H4O2)C6H3 (9k)[d]
2-MeOC6H4 (9l)
2-MeOC6H4 (9l)
2-MeC6H4 (9m)
2-ClC6H4 (9n)
2-ClC6H4 (9n)
2-ClC6H4 (9n)
2-CF3C6H4 (9o)
2-Me-4-MeOC6H3 (9p)
2,4-Cl2C6H3 (9q)
2,4-Cl2C6H3 (9q)
2,4-Cl2C6H3 (9q)
2-MeO-5-BrC6H3 (9r)
1-naphthyl (9s)
2-furyl (9t)
9
10
11
12
13
14
15
16
17
18[b]
19[b]
20[b]
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
13ja
13jg
13kg
13lg
13ld
13md
13na
13nh
13nd
13oa
13pg
13qa
13qg
13qd
13rg
13sg
13ta
13tg
13th
13td
13ug
96
85
98
98
94 (S)
99
75 (S)
95
98
94
C6H5 (12g)
4-MeOC6H4 (12a)
C6H5 (12g)
3-MeOC6H4 (12h)
4-CF3C6H4 (12d)
C6H5 (12g)
2-furyl (9t)
2-furyl (9t)
2-furyl (9t)
2-benzofuranyl (9u)
[a]
A mixture of aldimine (0.5 mmol), Ar2B(OH)2 (0.75 mmol), Rh complex (3 mol%) and N-Me-BIPAM (3.3 mol%) in
DME (2 mL) was stirred at 508C for 16 h.
at 808C.
3,4-Methylenedioxyphenyl.
[b]
[c]
[d]
2,3-DihydrobenzoACTHNUTRGENUGN[1,4]dioxine-6-yl.
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An N-Linked Bidentate Phosphoramidite Ligand (N-Me-BIPAM)
Table 3. Arylation of N-nosylimines (10, Scheme 1).[a]
FULL PAPERS
Entry
Ar1
Ar2
Product
Yield [%]
ee [%]
1
2
3
4
5
6
7
8
4-MeOC6H4 (10a)
4-ClC6H4 (10b)
4-ClC6H4 (10b)
4-ClC6H4 (10b)
4-ClC6H4 (10b)
3-ClC6H4 (10c)
3-ClC6H4 (10c)
2-ClC6H4 (10d)
2-ClC6H4 (10d)
C6H5 (12g)
14ag
14ba
14bd
14bh
14bi
14ca
14cd
14dd
14dh
14ed
14fg
14gd
72
91
89
97
99
76
84
99
88
81
99
90
93 (S)
97
97
97
97
96
97
98
98
4-MeOC6H4 (12a)
4-CF3C6H4 (12d)
3-MeOC6H4 (12h)
4-Br-3-FC6H3 (12i)
4-MeOC6H4 (12a)
4-CF3C6H4 (12d)
4-CF3C6H4 (12d)
3-MeOC6H4 (12h)
4-CF3C6H4 (12d)
C6H5 (12g)
9
10
11
12
2-MeOC6H4 (10e)
2-Me-4-MeOC6H3 (10f)
5-Br-2-MeOC6H3 (10g)
94
97
96
4-CF3C6H4 (12d)
[a]
A mixture of aldimine (0.5 mmol), Ar2B(OH)2 (0.75 mmol), Rh complex (3 mol%) and N-Me-BIPAM (3.3 mol%) in
DME (2 mL) was stirred at 508C for 16 h.
in low conversion (ca. 30%) due to slow transmetala- 2-formylbenzoate N-tosylimine (20) with a chiral
tion to the catalyst.
diene ligand followed by lactamization.[8]
The N-nosyl group (4-NO2C6H4SO2) is a alternative
This substrate possessing an ortho-ester group was
protecting group because of the mild conditions for found to be a suitable substrate for N-Me-BIPAM
its deprotection.[14] Although a retarding effect of a (Table 4). The representative arylboronic acids
polar nitro group has been reported in an analogous achieved quantitative yields and high enantioselectivi-
rhodium-catalyzed arylation of aldehydes,[15] addition ties in the range of 97–99% ee.
to N-nosylimines smoothly proceeded at 508C with
Numerous analogues of cryptostylines have been
high enantioselectivities in a range of 96–98% ee. The studied as pharmacological probes such as the D1
selectivities were comparable to those of N-tosyl- dopamine receptor, an antagonist of substance P and
A
a peptide neurotransmitter. The protocol shown in
Table 4 readily provided a simple access to such enan-
tiopure cryptostylines[17] (Scheme 3). A key intermedi-
ate (23) for synthesis of cryptostyline II was obtained
by enantioselective arylation of 22. The reaction at
Synthetic Applications
Chiral isoindolinones (21) are valuable drug candi- 508C was slow, but 23 was formed in good yield at
dates that are difficult to access by the catalytic proto- 808C with 98% ee. In the same manner, 24 for synthe-
col.[16] An elegant synthesis of a chiral isoindolinone sis of cryptostyline I was obtained by enantioselective
was first demonstrated by Lin via arylation of methyl arylation of 22 with 12o (71%, 98% ee). Lactamiza-
tion to 25 via deprotection of the nosyl group with
Table 4. Synthesis of 3-aryl-N-tosylphthalimidines.[a]
Entry
12, Ar2
Product
Yield [%]
ee [%]
1
2
3
4
5
4-MeOC6H4 (12a)
3-BrC6H4 (12j)
3-CF3C6H4 (12k)
3-F-4-MeOC6H3 (12l)
21a
21b
21c
21d
21e
97
98
98
94
96
98 (S)
97
97
97
99
2,3-dihydrobenzo
N
[a]
A mixture of aldimine (0.5 mmol), PhB(OH)2 (0.75 mmol), Rh complex (3 mol%) and N-Me-BIPAM (3.3 mol%) in
DME (2 mL) was stirred at 508C for 16 h. The reaction mixture was then treated with aqueous K2CO3 (1M, 2 mL) for
2 h at 508C.
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Kazunori Kurihara et al.
FULL PAPERS
Figure 2. A top view of RhACTHNUTRGNE(NUG acac)(N-Me-BIPAM) obtained
by DFT calculation.
arylrhodium(I)-phosphine intermediate. Thus, the S
and R configurations in Tables and 23 and 24 in
Scheme 3 obtained by (R,R)-N-Me-BIPAM are ra-
tionalized by the coordination of an imine with its si-
face.
No X-ray structure is yet available because of the
difficulty in synthesizing
a
single crystal of
Rh(acac)(N-Me-BIPAM). We therefore estimated
AHCTUNGTRENNUNG
this conformation by DFT computations on the
B3LYP/6–31G//B3LYP/LANL2DZ level of theory. A
top view of the stable complex (28) is shown in
Figure 2. The stable conformation displays a slightly
Scheme 3. Synthesis of cryptostyline II.
K2CO3 resulted in a complex mixture of products, but twisted square-planar coordination geometry for the
quantitative yield was achieved when 23 was treated rhodium(I) atom ligated with two phosphorus atoms
with 4-MeOC6H4SH and K2CO3 at 508C in CH3CN/ of N-Me-BIPAM and two oxygen atoms of acetylace-
DMSO (49/1) (97%).[18] Reduction of the carbonyl tone. The substituents on the left and right phospho-
group with BH3·Me2S was followed by methylation of rus atoms are not symmetrical. Although there is no
the N-H group with MeI and NaH to furnish (S)-(+)- large difference in steric hindrance between the upper
cryptostyline II in 45% yield. The absolute configura- and lower left areas, an equatorial NMe2 group blocks
tion of the product thus obtained by (R,R)-N-Me- the lower right area.
BIPAM ([a]D: +54.5, CHCl3) was established to be R
by the specific rotation reported for (S)-(+)-cryptos-
The stable conformation of the [Rh(Ph)
ACHTUNGTRENNUNG(OH2)
AHCTUNGTREGUN(NN (R,R)-N-Me-BIPAM)] intermediate generated by
tyline II ([a]D: +58.0, CHCl3).[17a] Thus, the product transmetalation of phenylboronic acid to Rh(OH)-
was produced by the mode of face selection as for
products shown in Table 2, Table 3, and Table 4.
ACHTUNGTRENUN(GN OH2)(N-Me-BIPAM) was calculated on the basis of
theoretical modeling. A top view (29) is shown in
Figure 3. There is a completely planar coordination
space in the left area consisting of a phenyl group on
the rhodium atom. A naphthyloxy group in the upper
right occupies a pseudo-axial position in the chelate
Enantioselection Mechanism
The catalytic cycle involves (i) transmetalation of an ring, whereas the lower right NMe2 group is in a
arylboronic acid to an HO-[Rh] complex giving an pseudo-equatorial position, thus suggesting that the
Ar-[Rh] species, (ii) insertion of an imine C=N bond space is accessible to reactants in the upper right
À
into the Ar Rh bond and finally (iii) formation of a quadrant and two quadrants in the left area.
diarylamine via hydrolysis of the Rh-N intermediate
On the basis of this calculation, a mode of coordi-
nation of the imine substrate to the current phenyl-
with water.[2,5]
The absolute configuration and enantioselectivity rhodium(I) intermediate is proposed in 30. The si-co-
are determined at the insertion step of imines into an ordination of the substrate is preferred without signif-
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An N-Linked Bidentate Phosphoramidite Ligand (N-Me-BIPAM)
FULL PAPERS
Experimental Section
Synthesis of N-Me-BIPAM (19, Scheme 2)
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
dry toluene were stirred for 2 days at 308C under nitrogen.
The crude solid obtained by evaporation of the solvent was
purified by column chromatography to give (R,R)-N-Me-
BIPAM as a white solid. 73%; [a]2D2: À578.3 (c 0.56, CHCl3);
1H NMR (400 MHz, CD2Cl2): d=8.32 (s, 2H), 7.93 (q, J=
9.1 Hz, 6H), 7.36–7.41 (m, 4H), 7.18–7.29 (m, 8H), 4.09 (d,
J=15.4 Hz, 2H), 3.76 (d, J=15.4 Hz, 2H), 2.58 (s, 3H), 2.32
(s, 6H), 2.30 (s, 6H); 13C NMR (CD2Cl2): d=149.5, 149.4,
148.6, 132.9, 131.5, 130.9, 129.8, 129.3, 128.2, 127.6, 127.3,
126.9, 126.4, 125.5, 124.8, 124.0, 122.7, 122.6, 121.1, 57.3,
44.5, 36.1, 34.8; 31P NMR (100 MHz, CD2Cl2): d=149.5;
HR-MS (FAB): m/z=774.2667, calcd. for C47H42N3O4P2
(M+H): 774.2651.
General Procedure for Rhodium-Catalyzed Arylation
of Aldimines with Arylboronic Acids (13 in Table 2
and 14 in Table 3)
A flask was charged with RhACHTNUGRTENNUG(acac)ACHTUNGTRNE(NGUN C2H4)2 (0.015 mmol, 3
mol%) and N-Me-BIPAM (19, 0.0165 mmol, 3.3 mol%)
under a nitrogen atmosphere. DME (2 mL) was added and
the mixture then stirred at room temperature for 30 min.
Arylboronic acid (0.75 mmol) and aldimine (9 or 10,
0.5 mmol) were added to this catalyst solution. After being
stirred for 16 h at 508C, the product was extracted with
ethyl acetate, washed with brine and dried over MgSO4.
Chromatography on silica gel with hexane/ethyl acetate
gave the product as white or yellow solids.
Figure 3. A top view of Rh(Ph)ACHTUNRGTNEUNG(OH2)(N-Me-BIPAM) ob-
tained by DFT calculation (29) and a proposed coordination
mode.
Characterization data of known compounds are given
below.
13aa: 85% ee, [a]D25: +7.01 (c 0.38, CHCl3);[7a] 13ab: 84%
ee, [a]2D5: +9.65 (c 0.41, CHCl3);[4] 13ac 95% ee, [a]2D5: +4.11
(c 0.32, CH3Cl);[7a] 13ad: 90% ee, [a]2D5: À6.11 (c 0.47,
icant steric interaction for giving the experimentally
observed S enantiomer by parallel coordination of the
À
C=N double bond to the Ph Rh bond for the next in-
sertion process. In mode 30, the efficiency of N-Me- CHCl3);[7a] 13af: 93% ee, [a]2D2: +1.09 (c 0.13, CHCl3);[4]
13bg: 94% ee, [a]D22: À6.34 (c 0.11, CHCl3);[7a] 13ca: 96% ee,
BIPAM for arylimines can be interpreted by parallel
orientation or p-p stacking of the two aryl groups on
the rhodium atom and imine substrate. On the other
hand, the coordination of an imine from its opposite
re face is being blocked by the equatorial NMe2
group.
[a]2D5: +4.08 (c 0.20, CHCl3);[8] 13cg: 96% ee, [a]2D5: À12.8 (c
0.34, CH3Cl);[4] 13da: 98% ee, [a]D25: +10.2 (c 0.39, CHCl3);[8]
13dg: 95% ee, [a]D22: À9.87 (c 0.29, CHCl3);[8] 13eg: 94% ee,
25
[a]D25: À11.5 (c 0.47, CHCl3);[8] 13fg: 96% ee, [a]D À3.39 (c
0.14, CHCl3);[7a] 13gg: 99% ee, [a]2D5: +1.94 (c 0.38,
CHCl3);[4] 13lg: 18% ee, [a]D25: À6.77 (c 0.41, CHCl3);[4] 13na
(96% ee, [a]D24: +32.9 (c 0.28, CHCl3);[8] 13sg: 94% ee, [a]2D5:
+4.25 (c 0.13, CHCl3);[7a] 13tg: 75% ee, [a]2D5: À10.8 (c 0.37,
CHCl3);[7a] 14ag: 93% ee, [a]D25: +13.8 (c 0.34, THF);[7b] 21a:
98% ee, [a]2D5: +25.2 (c 0.48, CHCl3).[8]
Conclusion
Characterization data of new compounds are given below.
13ae: [a]2D2: +2.47 (c 0.38, CHCl3), 97% ee (Chiralcel OD-
H, hexane/2-propanol=4/1, flow=0.5 mLminÀ1, wave-
In conclusion, we have developed a new chiral biden-
tate phosphoramidite ligand (N-Me-BIPAM) that is
highly efficient for asymmetric arylation of both N-
tosyl and N-nosylarylimines with arylboronic acids.
With this catalyst system, a broad range of enantio-
pure diarylmethylamines were easily prepared by
using a minimum amount of arylboronic acid. Studies
on further applications of N-Me-BIPAM to other C
C bond-forming reactions are in progress in our
group.
1
length=230 nm, tR =19.6 and 27.1 min); H NMR (CDCl3):
d=7.54 (d, J=8.7 Hz, 2H), 7.22–7.18 (m, 3H), 7.14 (d, J=
8.2 Hz, 1H), 7.06–7.03 (m, 2H), 6.86–6.74 (m, 3H), 5.47 (d,
J=7.2 Hz, 1H), 5.14 (d, J=7.2 Hz, 1H), 3.82 (s, 3H) 2.37 (s,
3H); 13C NMR
ACTHUNTRGNE(UGN CDCl3): d=153.3, 150.9, 147.1, 147.0, 143.4,
À
140.2, 137.2, 129.4, 128.7, 127.8, 127.2, 123.3, 115.4, 115.2,
113.2, 60.5, 56.3, 21.5; HR-MS (EI): m/z=385.1155, calcd.
for C21H20FNO3S: 385.1148.
Adv. Synth. Catal. 2009, 351, 260 – 270
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
265

Kazunori Kurihara et al.
FULL PAPERS
13dd: [a]2D5: À13.6 (c 0.56, CHCl3), 92% ee (Chiralpak IB,
hexane/ethanol=95/5, flow=0.8 mLminÀ1, wavelength=
230 nm, tR =24.5 28.1 min); 1H NMR (CDCl3): d=7.52 (d,
J=8.2 Hz, 2H), 7.45 (d, J=8.2 Hz, 2H), 7.20 ( d, J=8.6 Hz,
4H), 7.14 (d, J=8.2 Hz, 2H), 6.99 (d, J=8.6 Hz, 2H), 5.59
(d, 7.2 Hz, 1H), 4.98 (d, 7.2 Hz, 1H), 2.38 (s, 3H), 2.16 (s,
3H); 13C NMR (CDCl3): d=143.8, 138.2, 136.9, 134.1, 129.5,
129.0, 128.7, 127.7, 127.1, 125.6, 60.4, 21.5; HR-MS (ESI):
m/z=462.0515, calcd. for C18H17ClF3NO2SNa (M+Na):
462.0518.
13ld: [a]2D3: À29.99 (c 0.43, CHCl3), 98% ee (Chiralpak IB,
hexane/ethanol=9/1, flow=0.5 mLminÀ1, wavelength=
230 nm, tR =20.4 and 31.5 min); H NMR (CDCl3): d=7.50
1
(d, J=8.2 Hz, 2H), 7.44 (d, J=8.2 Hz, 2H), 7.31 (d, J=
8.2 Hz, 2H), 7.17 (ddd, J=1.4, 7.7 and 8.2 Hz, 1H), 7.04 (d,
J=8.2 Hz, 1H), 6.93 (d, J=7.7 Hz, 1H), 7.77 (dd, J=7.7
and 8.2 Hz, 1H), 6.68 (d, J=8.2 Hz, 1H), 5.95 (d, J=9.5 Hz,
1H), 5.65 (d, J=9.5 Hz, 1H), 3.58 (s, 3H) 2.31 (s, 3H);
13C NMR (CDCl3): d=156.2, 144.7, 143.1, 137.3, 129.6,
129.5, 129.2, 127.2, 127.0, 125.1, 120.8, 111.2, 58.8, 55.3, 31.0,
21.5; HR-MS (EI): m/z=435.1123, calcd. for C22H20F3NO3S:
435.1116.
13hg: [a]2D4: +1.45 (c 0.42, CHCl3), 97% ee (Chiralpak IB,
hexane/ethanol=99/1, flow=0.8 mLminÀ1, wavelength=
1
13md: [a]2D2: À8.46 (c 0.44, CHCl3), 93% ee (Chiralpak IB,
230 nm, tR =44.9 and 46.3 min); H NMR (CDCl3): d=7.54
hexane/ethanol=95/5, flow=0.5 mLminÀ1, wavelength=
(d, J=8.2 Hz, 2H), 7.23–7.12 (m, 7H), 7.08–7.00 (m, , 4H),
5.52 (d, J=6.8 Hz, 1H), 5.07 (d, J=6.8 Hz, 1H), 2.32 (s,
3H); 13C NMR (CDCl3): d=143.6, 142.4, 139.9, 137.1, 134.4,
129.8, 129.5, 128.8, 128.0, 127.7, 127.6, 128.8, 128.0, 127.7,
127.6, 127.3, 127.2, 125.6, 60.9, 21.6; HR-MS (ESI): m/z=
394.0634, calcd. for C20H18ClNO2SNa (M+Na): 394.0644.
13ig: [a]24: À16.41 (c 0.51, CHCl3), 92%ee (Chiralpak IB,
hexane/ethDanol=9/1, flow=1.0 mLminÀ1, wavelength=
1
230 nm, tR =17.7 and 36.0 min); H NMR (CDCl3): d=7.51
(d, J=8.6 Hz, 2H), 7.42 (d, J=8.2 Hz, 2H), 7.22 (d, J=
7.7 Hz, 2H), 7.16–7.03 (m, 5H), 6.95 (d, J=7.7 Hz, 1H),
5.84 (d, J=6.8 Hz, 1H), 5.10 (d, J=6.8 Hz, 1H), 2.36 (s,
3H), 2.19 (s, 3H); 13C NMR (CDCl3): d=144.0, 143.6, 137.6,
137.2, 135.7, 131.0, 129.4, 127.3, 127.1, 126.5, 125.5, 125.4,
57.7, 21.5, 19.4; HR-MS (EI): m/z=418.1077, calcd. for
C22H19F3NO2S (MÀH): 418.1089.
1
230 nm, tR =19.6 and 25.0 min); H NMR (CDCl3): d=7.53
(d, J=8.6 Hz, 2H), 7.23–7.01 ( m, 9H), 6.71 (d, J=8.2 Hz,
1H), 6.61 (d, J=2.7 Hz, 1H), 6.65 (dd, J=8.2 Hz, 1H),5.47
(d, 9.1 Hz, 1H), 5.16 (d, J=9.1 Hz, 1H), 3.82 (s, 3H), 2.38
(s, 3H); 13C NMR (CDCl3): d=155.3, 143.5, 140.2, 137.2,
134.0, 132.3, 129.5, 128.8, 127.9, 127.7, 127.3, 127.2, 111.7,
60.4, 56.3, 21.6; HR-MS (EI): m/z=445.0338, calcd for
C21H20BrNO2S: 445.0347.
13nh: [a]2D4: À78.35 (c 0.51, CHCl3), 96% ee (Chiralcel
AS-H, hexane/2-propanol=7/3, flow=0.7 mLminÀ1, wave-
1
length=230 nm, tR =39.5 and 46.5 min); H NMR (CDCl3):
d=7.6 (d, J=8.2 Hz, 2H), 7.33 (dd, J=3.6, 5.4 Hz, 1H),
7.22–7.19 (m, 1H), 7.15–7.10 (m, 4H), 6.73 (dd, J=1.8,
8.2 Hz, 1H), 6.62 (d, J=7.7 Hz, 1H), 6.59 (d, J=1.8 Hz,
1H), 5.87 (d, J=7.7 Hz, 1H), 5.40 (d, J=7.7 Hz, 1H), 3.67
(s, 3H), 2.36 (s, 3H); 13C NMR (CDCl3): d=159.7, 143.4,
140.9, 137.5, 137.0, 132.8, 129.9, 129.5, 129.3, 128.9, 127.3,
127.0, 119.5, 113.2, 113.1, 58.5, 55.2, 21.5; HR-MS (EI):
m/z=401.0866, calcd. for C21H20ClNO3S: 401.0852.
13ja: [a]24: À90.2 (c 0.52, CHCl3), 97% ee (Chiralcel OB-
H, hexanDe/2-propanol=4/1, flow=0.8 mLminÀ1, wave-
1
length=230 nm, tR =21.6 and 35.7 min); H NMR (CDCl3):
d=7.55 (d, J=8.2 Hz, 2H), 7.16 (d, J=8.2 Hz, 9H), 6.98 (d,
J=8.6 Hz, 1H) 6.73 (dd, 2.2, 6.8 Hz, 2H), 6.63 (d, J=
7.7 Hz, 1H), 6.58–6.52 (m, 2H), 5.88 (dd, J=1.4 and 5.0 Hz,
2H), 5.41 (d, J=6.3 Hz, 1H), 4.83 (d, J=6.3 Hz, 1H), 3.75
(s, 3H), 2.38 (s, 3H); 13C NMR (CDCl3): d=159.0, 147.8,
146.9, 143.2, 137.4, 134.8, 132.7, 129.4, 128.5, 127.3, 120.9,
113.9, 108.1, 107.9, 101.1, 60.5, 55.3, 21.6; HR-MS (EI):
m/z=411.1139, calcd. for C22H21NO5S: 411.1140.
13nd: [a]2D3: +2.03 (c 0.45, CHCl3), 96% ee (Chiralcel OD-
H, hexane/2-propanol=9/1, flow=0.8 mLminÀ1, wave-
1
length=230 nm, tR =12.0 and 25.9 min); H NMR (CDCl3):
d=7.57 (d, J=8.8 Hz, 2H), 7.47 (d, J=8.2 Hz, 1H), 7.25–
7.12 (m, 8H), 5.95 (d, J=7.2 Hz, 1H), 5.32 (d, J=7.2 Hz,
1H), 2.36 (s, 3H); 13C NMR (CDCl3): d=143.7, 143.3, 136.9,
136.8, 131.6, 130.2, 129.5, 129.4, 127.6, 129.4, 127.6, 127.3,
127.2, 125.6, 125.5, 58.4, 21.5; HR-MS (ESI): m/z=462.0519,
calcd. for C21H17ClF3NO2SNa (M+Na): 462.0518.
13jg: [a]2D4: À17.85 (c 0.54, CHCl3), 85% ee (Chiralcel
OD-H, hexane/2-propanol=9/1, flow=0.5 mLminÀ1, wave-
1
length=230 nm, tR =44.0 and 48.2 min); H NMR (CDCl3):
13oa: [a]2D3: À78.61 (c 0.43, CHCl3), 96% ee (Chiralpak IB,
d=7.55 (d, J=8.1 Hz, 2H), 7.21–7.18 (m, 3H), 7.15 (d, J=
8.1 Hz, 2H) , 7.09 (dd, J=2.3 and 7.3 Hz, 2H), 6.63 (d,
3.2 Hz, 1H), 6.57–6.52 (m, 2H), 5.88 (dd, J=1.4 and 4.0 Hz,
2H), 5.46 (d, J=6.8 Hz, 1H), 4.96 (d, J=5.8 Hz, 1H), 2.38
(s, 3H); 13C NMR (CDCl3): d=147.8, 147.1, 143.3, 140.5,
137.3, 134.5, 129.4, 128.6, 127.7, 127.3, 127.2, 121.0, 108.1,
107.9, 101.2, 61.2, 21.6; HR-MS (EI): m/z=381.1035, calcd.
for C21H19NO4S: 381.1035.
hexane/2-propanol=9/1, flow=0.8 mLminÀ1, wavelength=
1
230 nm, tR =18.9 and 27.5 min); H NMR (CDCl3): d=7.65
(d, J=8.1 Hz, 1H), 7.62 (d, J=8.1 Hz, 2H), 7.57 (d, J=
7.7 Hz, 1H), 7.47 (t, J=7.7 Hz, 1H), 7.33 (t, J=7.7 Hz, 1H),
7.19 (d, J=8.1 Hz, 2H), 5.87 (d, J=5.4 Hz, 1H), 4.96 (d, J=
5.4 Hz, 1H), 3.73 (s, 3H),2.40 (s, 3H); 13C NMR (CDCl3):
d=159.2, 143.5, 138.9, 136.7, 132.1, 132.0, 129.4, 128.8, 127.6,
127.4, 114.0, 56.6, 55.3, 21.6; HR-MS (EI): m/z=435.1121,
calcd. for C22H20F3NO3S: 435.1116.
13kg: [a]2D4: À18.7 (c 0.51, CHCl3), 99% ee (Chiralpak IB,
hexane/ethanol=95/5, flow=0.5 mLminÀ1, wavelength=
13pg: [a]2D2: À9.76 (c 0.56, CHCl3); 88% ee (Chiralpak IB,
1
230 nm, tR =59.1 and 63.8 min); H NMR (CDCl3): d=7.55
hexane/ethanol=95/5, flow=0.5 mLminÀ1, wavelength=
(d, J=8.2 Hz, 2H), 7.21–7.17 (m, 3H), 7.15 (d, J=8.6 Hz,
1H), 7.10–7.08 (m, 2H), 6.68 (d, 8.6 Hz, 1H), 6.55 (dd, J=
2.3 and 7.7 Hz, 1H), 6.54 (s, 1H), 5.43 (d, J=6.8 Hz, 1H),
4.95 (d, J=6.8 Hz, 1H), 4.19–4.16 (m, 4H), 2.37 (s, 3H);
1
230 nm, tR =28.3 and 32.5 min); H NMR (CDCl3): d=7.53
(d, J=8.1 Hz, 2H), 7.45 (d, J=8.2 Hz, 2H), 7.17–7.20 (m,
3H), 7.11 (d, J=8.1 Hz, 2H), 7.04–7.06 (m, 2H), 6.96 (d, J=
8.6 Hz, 1H), 6.61 (d, J=2.8 Hz, 1H), 6.55 (dd, J=2.8,
8.2 Hz, 1H), 5.72 (d, 6.8 Hz, 1H), 5.04 (d, 6.8 Hz, 1H), 3.73
(s, 3H), 2.36 (s, 3H), 2.13 (s, 3H); 13C NMR (CDCl3): d=
155.8, 143.1, 140.4, 137.5, 137.1, 130.7, 129.4, 128.7, 128.5,
13C NMR
ACHTUNGTRENNUNG(CDCl3): d=143.4, 143.2, 143.0, 140.6, 137.4, 133.9,
129.4, 128.5, 127.6, 127.3, 120.5, 117.3, 116.5, 64.3, 60.9, 21.6;
HR-MS (EI): m/z=395.1207, calcd. for C22H21NO4S:
395.1191.
266
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ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2009, 351, 260 – 270

An N-Linked Bidentate Phosphoramidite Ligand (N-Me-BIPAM)
FULL PAPERS
127.5, 127.2, 116.2, 111.2, 57.8, 55.2, 21.5, 19.6; HR-MS (EI):
HR-MS (EI): m/z=357.1024, calcd. for C19H19NO4S:
357.1035.
m/z=381.1396, calcd. for C22H23NO3S: 381.1399.
13qa: [a]2D3: À75.11 (c 0.46, CHCl3), 96% ee (Chiralpak IB,
13th: [a]2D4: À150.71 (c 0.32, CHCl3), 95% ee (Chiralcel
hexane/2-propanol=9/1, flow=0.8 mLminÀ1, wavelength=
AD-H, hexane/2-propanol=4/1, flow=0.5 mLminÀ1, wave-
1
1
230 nm, tR =19.5 and 28.7 min); H NMR (CDCl3): d=7.59
length=230 nm, tR =32.5 and 34.5 min); H NMR (CDCl3):
(d, J=8.6 Hz, 2H), 7.34 (d, J=8.2 Hz, 1H), 7.22 (d, J=
2.3 Hz, 1H), 7.18 (d, J=8.6 Hz, 2H), 7.11 (dd, J=2.3 and
8.6 Hz 1H), 6.90 (d, J=8.6 Hz, 2H), 6.73 (d, J=8.6 Hz,
2H), 5.77 (d, 6.8 Hz, 1H), 5.33 (d, 6.8 Hz, 1H), 3.72 (s, 3H),
2.39 (s, 3H); 13C NMR (CDCl3): d=159.3, 143.8, 136.8,
136.5, 133.9, 133.4, 130.8, 130.0, 129.6, 128.6, 127.3, 114.2,
57.7, 55.3, 21.6; HR-MS (EI): m/z=435.0467, calcd. for
C21H19Cl2NO2S: 435.0463.
d=7.56 (d, J=8.6 Hz, 2H), 7.20 (d, J=1.8 Hz, 1H), 7.18–
7.09 (m, 3H), 6.74 (d, J=8.2 Hz, 2H), 6.68 (d, J=1.8 Hz,
1H), 6.16 (dd, J=1.8 and 3.2 Hz, 1H), 6.00 (d, J=3.2 Hz,
1H), 5.57 (d, J=7.7 Hz, 1H), 5.46 (d, J=7.7 Hz, 1H), 3.68
(s, 3H), 2.36 (s, 3H); 13C NMR (CDCl3): d=159.8, 152.1,
143.2, 142.6, 139.7, 137.3, 129.7, 127.2, 119.6, 113.7, 112.7,
110.3, 108.4, 55.5, 55.2, 21.5; HR-MS (EI): m/z=357.1020,
calcd. for C19H19NO4S: 357.1035.
13qg: [a]2D2: +3.88 (c 0.43, CHCl3), 85% ee (Chiralpak IB,
13td: [a]2D3: À10.95 (c 0.56, CHCl3), 98% ee (Chiralcel
hexane/ethanol=95/5, flow=0.8 mLminÀ1, wavelength=
AD-H, hexane/2-propanol=4/1, flow=0.5 mLminÀ1, wave-
1
1
230 nm, tR =14.4 and 15.7 min); H NMR (CDCl3): d=7.60
length=230 nm, tR =16.5 and 17.2 min); H NMR (CDCl3):
(d, J=8.2 Hz, 2H), 7.32 (d, J=8.6 Hz, 1H), 7.21–7.25 (m,
4H), 7.18 (d, J=8.2 Hz, 2H), 7.13 (dd, J=2.8, 8.2 Hz 1H),
7.00–7.03 (m, 2H), 5.83 (d, 6.8 Hz, 1H), 5.20 (d, 6.8 Hz,
1H), 2.40 (s, 3H); 13C NMR (CDCl3): d=143.8, 138.8, 136.7,
136.3, 134.1, 133.5, 130.3, 129.6, 128.9, 128.2, 127.3, 58.2,
d=7.53 (d, J=8.6 Hz, 2H), 7.45 (d, J=8.2 Hz, 2H), 7.30 (d,
J=8.2 Hz, 2H), 7.12 (d, J=8.6 Hz, 2H), 6.20 (dd, J=1.8
and 3.2 Hz, 1H), 5.97 (d, J=3.2 Hz, 1H), 5.65 (d, J=7.3 Hz,
1H), 5.49 (d, J=7.3 Hz, 1H), 2.35 (s, 3H); 13C NMR
(CDCl3): d=151.2, 143.6, 143.0, 142.0, 137.0, 129.5, 127.8,
127.1, 125.5, 125.4, 110.4, 108.8, 55.2, 21.5; HR-MS (EI):
m/z=395.0806, calcd. for C19H16F3NO3S: 395.0803.
21.6;
HR-MS
(ESI):
m/z=428.0239,
calcd.
for
C20H17Cl2NO2SNa (M+Na): 428.0255.
13qd: [a]2D3: À100.84 (c 0.50, CHCl3), 98% ee (Chiralpak
14ba: [a]2D3: +12.04 (c 0.56, THF), 97% ee (Chiralcel OD-
IB, hexane/2-propanol=9/1, flow=0.8 mLminÀ1, wave-
H, hexane/ethanol=9/1, flow=1.0 mLminÀ1, wavelength=
1
length=230 nm, tR =18.0 and 20.0 min); H NMR (CDCl3):
1
230 nm, tR =37.0 and 41.4 min); H NMR (CDCl3): d=8.14
d=7.57 (d, J=8.1 Hz, 2H), 7.48 (d, J=8.1 Hz, 1H), 7.26–
7.13 ( m, 8H), 7.18 (d, J=8.6 Hz, 2H), 5.89 (d, 7.2 Hz, 1H),
(d, J=8.6 Hz, 2H), 7.76 (d, J=9.1 Hz, 2H), 7.19 (d, J=
8.6 Hz, 2H), 7.07 (d, J=8.6 Hz, 2H), 6.92 (d, J=8.6 Hz,
2H), 6.71 (d, J=9.1 Hz, 2H), 5.62 (d, J=7.3 Hz, 1H), 5.28
(d, J=7.3 Hz, 1H), 3.72 (s, 3H); 13C NMR (CDCl3): d=
159.7, 149.8, 146.2, 138.4, 134.0, 131.1, 128.9, 128.7, 128.6,
128.4, 124.0, 114.2, 60.6, 55.4; HR-MS (EI): m/z=432.0546,
calcd. for C20H17ClN2O5S: 432.0547.
5.33 (m, 1H), 2.39 (s, 3H); 13C NMR
ACHTNUTRGNE(UNG CDCl3): d=144.0,
142.7, 136.6, 135.5, 135.4, 134.7, 133.5, 130.2, 129.9, 129.6,
128.7, 128.5, 128.3, 128.1, 127.6, 127.2, 125.7, 57.9, 21.6; HR-
MS (ESI): m/z=496.0128, calcd. for C21H16Cl2F3NO2SNa
(M+Na): 496.0129.
13rg: [a]2D4: +1.26 (c 0.42, CHCl3), 98% ee (Chiralpak IB,
14bd: [a]2D3: À8.34 (c 0.59, THF), 97% ee (Chiralcel OD-
hexane/ethanol=95/5, flow=0.5 mLminÀ1, wavelength=
H, hexane/ethanol=9/1, flow=1.0 mLminÀ1, wavelength=
1
230 nm, tR =27.6 and 33.6 min); H NMR (CDCl3): d=7.50
1
230 nm, tR =26.9 and 39.1 min); H NMR ([D6]acetone): d=
(d, J=8.2 Hz, 2H), 7.25–7.14 (m, 6H), 7.08 (d, J=8.2 Hz,
2H), 6.97 (d, J=2.3 Hz, 1H), 6.54 (j, J=8.6 Hz, 1H) 5.64
(d, 9.1 Hz, 1H), 5.51 (d, J=9.1 Hz, 1H), 3.58 (s, 3H), 2.35
(s, 3H); 13C NMR (CDCl3): d=155.5, 143.3, 139.7, 137.1,
132.2, 131.4, 129.7, 129.3, 128.36, 127.4, 127.1, 126.7, 113.0,
112.8, 58.4, 55.7, 21.6; HR-MS (EI): m/z=445.0354, calcd.
for C21H20BrNO2S: 445.0347.
8.43–8.13 (m, 2H), 8.07–7.78 (m, 2H), 7.62 (d, J=8.2 Hz,
2H), 7.41 (d, J=8.2 Hz, 2H), 7.38–7.32 (m, 2H), 7.26–7.15
(m, 2H), 7.04 (s, 1H), 5.83 (s, 1H); 13C NMR(acetone-d6):
d=150.0, 146.3, 255.5, 138.6, 133.4, 129.4, 129.3, 129.1, 128.8,
128.5, 128.2, 125.6, 124.3, 122.9, 60.3; HR-MS (ESI): m/z=
469.0222, calcd. for C20H13ClF3N2O4S (MÀH): 469.0237.
14bh: [a]2D2: +4.88 (c 0.54, CHCl3), 97% ee (Chiralcel OD-
H, hexane/ethanol=9/1, flow=1.0 mLminÀ1, wavelength=
13ug: [a]2D3: À49.6 (c 0.45, CHCl3), 94% ee (Chiralpak IB,
hexane/ethanol=95/5, flow=0.5 mLminÀ1, wavelength=
1
1
230 nm, tR =22.7 and 45.9 min); H NMR (CDCl3): d=8.12
230 nm, tR =28.5 and 29.9 min); H NMR (CDCl3): d=7.56
(d, J=9.1 Hz, 2H), 7.76 (d, J=9.1 Hz, 2H), 7.19 (d, J=
8.6 Hz, 2H), 7.15–7.04 (m, 3H), 6.71 (dd, J=2.3 and 8.2 Hz,
1H), 6.60 (d, J=7.7 Hz, 1H), 6.49 (t, J=1.8 Hz, 1H), 5.61
(d, J=7.7 Hz, 1H), 5.43 (d, J=7.7 Hz, 1H), 3.66 (s, 3H);
13C NMR (CDCl3): d=159.9, 149.8, 146.1, 140.4, 138.0,
134.1, 130.1, 128.9, 128.8, 128.3, 123.9, 119.5, 113.6, 112.9,
61.0, 55.2; HR-MS (EI): m/z=432.0527, calcd. for
C20H17ClN2O5S: 432.0547.
(d, J=8.6 Hz, 2H), 7.40 (dd, J=1.3 and 6.8 Hz, 1H), 7.28–
7.13 (m, 8H), 6.99 (d, J=8.1 Hz, 2H), 6.40 (s, 1H), 5.73 (d,
J=8.2 Hz, 1H), 5.37 (d, J=8.2 Hz, 1H), 2.22 (s, 3H),
13C NMR (CDCl3): d=157.9, 157.3, 143.3, 137.6, 137.0,
129.2, 128.8, 128.4, 127.7, 127.3, 127.1, 124.4, 122.9, 121.1,
111.2, 105.6, 55.9, 21.4; HR-MS (EI): m/z=377.1091, calcd.
for C22H19NO3S: 377.1086.
13ta: [a]22: +2.79 (c 0.45, CHCl3), 99% ee (Chiralcel OD-
H, hexanDe/2-propanol=4/1, flow=0.5 mLminÀ1, wave-
14bi: [a]2D3: À2.28 (c 0.55, THF), 97% ee (Chiralcel OD-H,
hexane/ethanol=9/1, flow=0.7 mLminÀ1, wavelength=
1
length=230 nm, tR =21.6 and 23.8 min); H NMR (CDCl3):
1
230 nm, tR =49.0 and 52.2 min); H NMR (acetone-d6): d=
d=7.56 (d, J=8.2 Hz, 2H), 7.20 (s, 1H), 7.15 (d, J=8.2 Hz,
2H), 7.07 (d, J=8.6 Hz, 2H), 6.75 (d, J=8.6 Hz, 2H), 6.27–
6.08 (m, 1H), 5.98 (d, J=3.2 Hz, 1H), 5.54 (d, J=7.3 Hz,
1H), 5.23 (d, J=7.3 Hz, 1H), 3.89 (s, 3H), 2.53 (s, 3H);
13C NMR (CDCl3): d=159.3, 152.5, 143.2, 142.5, 137.4,
130.4, 129.4, 128.5, 127.2, 113.9, 110.2, 108.2, 55.3, 55.1, 21.6;
8.26 (d, J=8.6 Hz, 2H), 7.91 (d, J=8.6 Hz, 2H), 7.56 (t, J=
8.2 Hz, 2H), 7.34 (d, J=8.6 Hz, 2H), 7.19 (d, 8.6 Hz, 2H),
7.10–7.07 (m, 1H), 6.99–6.96 (m, 2H), 5.72 (s, 1H);
13C NMR (acetone-d6): d=160.0, 157.6, 150.0, 146.2, 142.5,
142.4, 138.4, 133.9, 133.5, 129.2, 128.8, 128.5, 124.9, 124.3,
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Kazunori Kurihara et al.
FULL PAPERS
115.8, 115.5, 107.8, 59.8; HR-MS (ESI): m/z=496.9362,
calcd. for C19H12BrClFN2O4S (MÀH): 496.9374.
116.4, 111.2, 58.1, 55.2, 19.7; HR-MS (EI): m/z=412.1085,
calcd. for C21H20N2O5S: 412.1093.
14gd: [a]2D2: À12.14 (c 0.47, CHCl3), 96% ee (Chiralcel
14ca: [a]22: +17.99 (c 0.55, CHCl3), 96% ee (Chiralcel
OD-H, heDxane/ethanol=9/1, flow=1.0 mLminÀ1, wave-
OD-H, hexane/ethanol=9/1, flow=1.0 mLminÀ1, wave-
1
1
length=230 nm, tR =17.4 and 48.5 min); H NMR (CDCl3):
length=230 nm, tR =34.7 and 65.1 min); H NMR (CDCl3):
d=8.13 (d, J=8.6 Hz, 2H), 7.78 (d, J=8.6 Hz, 2H), 7.51 (d,
J=8.2 Hz, 2H), 7.30 (d, J=8.2 Hz, 2H), 7.27–7.24 (m, 1H),
6.95 (d, J=2.8 Hz, 1H), 6.57 (d, J=8.6 Hz, 1H), 5.97 (d, J=
9.5 Hz, 1H), 5.64 (d, J=9.5 Hz, 1H), 3.60 (s, 3H); 13C NMR
(CDCl3): d=155.3, 149.9, 145.8, 142.9, 132.5, 132.3, 128.2,
128.0, 126.9, 125.5, 123.9, 113.2, 58.6, 55.9; HR-MS (EI):
m/z=543.9889, calcd. for C21H16BrF3N2O5S: 543.9915.
d=8.13 (d, J=9.1 Hz, 2H), 7.74 (d, J=9.1 Hz, 2H), 7.19–
7.11 (m, 2H), 7.02 (s, 1H), 6.96 (d, J=8.7 Hz, 2H), 6.72 (d,
J=8.7 Hz, 1H), 5.62 (d, J=6.8 Hz, 1H), 5.40 (d, J=6.8 Hz,
1H), 3.73 (s, 3H); 13C NMR (CDCl3): d=159.6, 146.1, 141.6,
134.7, 130.9, 130.0, 128.7, 128.3, 128.1, 127.4, 125.6, 123.9,
114.3, 60.8, 55.4; HR-MS (EI): m/z=432.0525, calcd. for
C20H17ClN2O5S: 432.0547.
15ag: [a]2D5: À12.5 (c 0.31, CHCl3), 87% ee (Chiralcel OD-
14cd: [a]2D2: À3.07 (c 0.52, THF), 97% ee (Chiralcel OD-
H, hexane/ethanol=9/1, flow=1.0 mLminÀ1, wavelength=
H, hexane/ethanol=9/1, flow=1.0 mLminÀ1, wavelength=
1
1
230 nm, tR =17.4 and 48.5 min); H NMR (CDCl3): d=7.37–
230 nm, tR =18.7 and 59.1 min); H NMR (CDCl3): d=8.16
7.21 (m, 5H), 7.22 (d, J=8.6 Hz, 2H), 6.87 (d, J=8.6 Hz,
2H), 5.70 (d, J=7.1 Hz, 1H), 5.05 (d, J=7.1 Hz, 1H), 3.78
(s, 3H), 2.64 (s, 3H), 13C NMR (CDCl3): d=159.3, 140.9,
132.7, 128.9, 128.7, 128.0, 127.4, 114.3, 60.8, 55.4, 42.0; HR-
MS (EI): m/z=291.0929, calcd. for C21H16BrF3N2O5S:
291.0929.
(d, J=9.1 Hz, 2H), 7.78 (d, J=8.6 Hz, 2H), 7.51 (d, J=
8.6 Hz, 2H), 7.26 (d, J=9.1 Hz, 2H), 7.23–7.15 (m, 2H),
6.98–6.95 (m, 2H), 5.72 (d, J=7.3 Hz, 1H) , 5.49 (d, J=
7.3 Hz, 1H); 13C NMR (CDCl3): d=150.0, 145.7, 142.8,
140.5, 135.1, 128.7, 128.3, 127.8, 127.5, 125.9, 125.6, 124.1,
60.8;
HR-MS
(ESI):
m/z=469.0224,
calcd.
for
C20H13ClF3N2O4S (MÀH): 469.0237.
14dd: [a]2D1: À0.90 (c 0.43, CHCl3), 98% ee (Chiralcel OD-
H, hexane/ethanol=9/1, flow=1.0 mLminÀ1, wavelength=
General Procedure for Synthesis of Isoindolinones
(21, Table 4):
1
230 nm, tR =12.4 and 37.9 min); H NMR (CDCl3): d=8.13
(d, J=8.6 Hz, 2H), 7.82 (d, J=9.1 Hz, 2H), 7.53 (d, J=
8.2 Hz, 2H), 7.30 (d, J=8.2 Hz, 2H), 7.26–7.07 (m, 4H),
6.07 (d, J=8.6 Hz, 1H), 5.77 (d, J=8.6 Hz, 1H); 13C NMR
(CDCl3): d=149.9, 145.6, 142.4, 135.8, 132.9, 130.5, 130.3,
129.4, 128.4, 127.2, 123.9, 119.4, 113.4, 113.0, 58.9, 55.3; HR-
MS (ESI): m/z=469.0221, calcd. for C20H13ClF3N2O4S
(MÀH): 469.0237.
A flask was charged with RhACHTNUGRTENNUG(acac)ACHTUNGTRNE(NGUN C2H4)2 (0.015 mmol, 3
mol%) and N-Me-BIPAM (19, 0.0165 mmol, 3.3 mol%)
under a nitrogen atmosphere. DME (2 mL) was added and
the mixture then stirred at room temperature for 30 min.
Arylboronic acid (0.75 mmol) and aldimine (20, 0.5 mmol)
were added to this catalyst solution. After being stirred for
16 h at 508C, the mixture was cooled to room temperature.
A solution of K2CO3 (2 mmol, 1M in H2O) was then added,
and the resulting mixture was stirred for 2 h at room tem-
perature. The product was extracted with ethyl acetate,
washed with brine and dried over MgSO4. Chromatography
on silica gel with hexane/ethyl acetate gave the product as a
white or yellow solids.
14dh: [a]2D3: +6.69 (c 0.42, CHCl3), 98% ee (Chiralcel OD-
H, hexane/ethanol=9/1, flow=1.0 mLminÀ1, wavelength=
1
230 nm, tR =16.3 and 24.4 min); H NMR (CDCl3): d=8.12
(d, J=8.6 Hz, 2H), 7.81 (d, J=8.6 Hz, 2H), 7.24–7.06 (m,
5H), 6.76 (dd, J=2.3, 8.2 Hz, 1H), 6.68 (d, J=7.7 Hz, 1H),
6.64 (s, 1H), 6.01 (d, J=7.7 Hz, 1H), 5.62 (d, J=7.7 Hz,
1H), 3.73 (s, 3H); 13C NMR (CDCl3): d=159.8, 149.8, 145.9,
139.9, 136.5, 133.0, 130.2, 129.9, 129.5, 129.4, 128.4, 127.2,
123.9, 119.4, 113.4, 113.0, 58.9, 55.3; HR-MS (EI): m/z=
432.0532, calcd. for C20H17ClN2O5S: 432.0547.
21a: Spectral data of 21a were as previously reported.[8]
21b: [a]2D2: À42.35 (c 0.54, CHCl3), 97% ee (AD-H,
hexane/2-propanol=7/3, flow=0.7 mLminÀ1, wavelength=
1
230 nm, tR =15.7 and 17.5 min); H NMR (CDCl3): d=7.86
14ed: [a]2D3: À39.92 (c 0.50, CHCl3), 94% ee (Chiralcel
(d, J=7.7 Hz, 1H), 7.59–7.46 (m, 4H), 7.43 (dt, J=1.8,
7.3 Hz, 1H), 7.21–7.15 (m, 5H), 6.96 (s, 1H), 6.14 (s, 1H),
2.38 (s, 3H); 13C NMR (CDCl3): d=166.3, 145.7, 145.2,
139.2, 135.8, 134.6, 131.9, 130.5, 130.4, 129.5, 129.4, 128.8,
128.0, 127.0, 125.0, 123.7, 122.9, 64.9, 21.8; HR-MS (ESI):
m/z=463.9930, calcd. for C21H16BrNO3SNa (M+Na):
463.9932.
OD-H, hexane/ethanol=9/1, flow=1.0 mLminÀ1, wave-
1
length=230 nm, tR =14.0 and 41.0 min); H NMR (CDCl3):
d=8.05 (d, J=8.8 Hz, 2H), 7.76 (d, J=8.8 Hz, 2H), 7.49 (d,
J=8.2 Hz, 2H), 7.32 (d, J=8.2 Hz, 2H), 7.17 (ddd, J=1.9,
7.7 and 8.2 Hz, 2H), 6.93 (d, J=7.3 Hz, 1H), 6.78 (ddd, J=
1.9, 7.3 and 7.7 Hz, 1H), 6.65 (d, J=8.2 Hz, 1H), 6.11 (t, J=
9.5 Hz, 1H), 5.7 (d, J=9.5 Hz, 1H), 3.59 (s, 3H); 13C NMR
(CDCl3): d=156.2, 149.7, 146.0, 130.1, 129.9, 128.1, 127.0,
125.8, 125.3, 123.7, 121.0, 111.5, 59.5; HR-MS (EI): m/z=
466.0819, calcd. for C21H17F3N2O5S: 466.0810.
21c: [a]23: +102.85 (c 0.50, CHCl3), 97% ee (AD-H,
hexane/ethDanol=99/1, flow=0.5 mLminÀ1, wavelength=
1
230 nm, tR =80.9 and 88.3 min); H NMR (CDCl3): d=7.88
(d, J=7.2 Hz, 1H), 7.59–7.40 (m, 7H), 7.13 (d, J=7.7 Hz,
4H), 6.25 (s, 1H), 2.34 (s, 3H); 13C NMR (CDCl3): d=166.3,
145.5, 145.2, 138.2, 135.7, 134.6, 131.8, 129.5, 129.4, 128.8,
125.6, 125.1, 124.2, 123.7, 77.3, 64.9, 21.5; HR-MS (ESI):
m/z= 454.0698, calcd. for C22H16F3NO3S (M+Na):
454.0701.
14fg: [a]2D3: À10.06 (c 0.47, THF), 97% ee (Chiralcel OD-
H, hexane/ethanol=9/1, flow=1.0 mLminÀ1, wavelength=
1
230 nm, tR =16.3 and 24.4 min); H NMR (CDCl3): d=8.08
(d, J=8.3 Hz, 2H), 7.71 (d, J=8.3 Hz, 2H), 7.19 (t, J=
3.2 Hz, 3H), 7.13–7.03 (m, 2H), 6.08 (d, J=8.6 Hz, 2H),
6.63 (d, J=2.8 Hz, 1H), 6.48 (dd, J=2.8 and 8.6 Hz, 1H),
5.90 (d, J=7.3 Hz, 1H), 5.13 (d, J=7.3 Hz, 1H), 3.71 (s,
3H), 2.25 (s, 3H); 13C NMR (CDCl3): d=159.1, 149.6, 146.4,
139.2, 137.5, 129.5, 128.7, 128.6, 128.2, 127.9, 127.5, 123.8,
21d: [a]2D2: À24.03 (c 0.51, CHCl3), 97% ee (Chiralcel AD-
H, hexane/2-propanol=7/3, flow=0.7 mLminÀ1, wave-
1
length=230 nm, tR =19.5 and 25.4 min); H NMR (CDCl3):
d=7.84 (d, J=7.7 Hz, 1H), 7.58–7.54 (m, 3H), 7.47 (dd, J=
268
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An N-Linked Bidentate Phosphoramidite Ligand (N-Me-BIPAM)
FULL PAPERS
7.4, 7.6 Hz, 1H), 7.16 (dd, J=7.7, 8.6 Hz, 3H), 7.00 (d, J=
8.2 Hz, 1H), 6.89 (dd, J=8.2 Hz, 8.6 Hz, 1H), 6.57 (dd, J=
1.8, 10.3 Hz, 1H), 3.89 (s, 3H), 2.36 (s, 3H); 13C NMR
(CDCl3): d=166.3, 153.5, 151.0, 148.1, 146.0, 145.0, 135.9,
134.5, 129.7, 129.3, 129.2, 128.8, 128.1, 124.9, 124.6, 123.7,
115.4, 115.2, 113.2, 64.8, 56.3, 21.7; HR-MS (EI): m/z=
411.0929, calcd. for C22H18FNO4S: 411.0941.
CH2Cl2 and washed with NH3Claq and brine, dried over
MgSO4. After concentration chromatography on silica gel
with hexane/ethyl acetate gave the cyclic product 25 as a
yellow solid; yield: 273 mg (97%). 1H NMR (CDCl3): d=
6.84 (s, 2H), 6.70 (s, 1H), 6.64 (s, 1H), 6.33 (s, 1H), 6.19
(brs, 1H), 5.52 (d, J=1.7 Hz, 1H), 3.88 (s, 3H) 3.87 (s, 3H),
3.81 (s, 3H), 3.68 (s, 3H) , 3.64 (s, 2H); 13C NMR (CDCl3):
d=170.6, 149.6, 149.2, 147.9, 134.1, 126.4, 123.1, 120.1, 111.1,
109.6, 60.0, 56.0, 35.8
21e: [a]2D3: À26.22 (c 0.42, CHCl3), 99% ee (AD-H,
hexane/2-propanol=7/3, flow=0.7 mLminÀ1, wavelength=
1
230 nm, tR =42.0 and 53.0 min); H NMR (CDCl3): d=7.82
(d, J=7.7 Hz, 1H), 7.62–7.49 (m, 3H), 7.44 (dd, J=7.3,
7.7 Hz, 1H), 7.16 (dd, J=7.3, 7.7 Hz, 3H), 6.73 (d, J=
Synthesis of Cryptostyline II (27, Scheme 3)
A
flask was charged with NaH (60% in oil, 70 mg,
1.75 mmol) and THF (5 mL). Then hexamethylphosphoric
acid amide (1.75 mmol) and 25 (400 mg, 1.17 mmol) in DMF
(5 mL) were added and then the mixture was stirred for
15 min at 08C. MeI (93 mL, 1.52 mmol) was then added at
08C, and the resulting mixture was stirred for 2 h at room
temperature. The product was treated with saturated NH3Cl
solution and extracted with CH2Cl2. The organic layer was
washed with brine and dried over MgSO4. After concentra-
tion, chromatography on silica gel with hexane/ethyl acetate
gave the N-methyl compound 26 as yellow oil; yield: 325 mg
(78%). 1H NMR (CDCl3): d=6.80 (s, 1H), 6.79 (d, J=
1.9 Hz, 1H), 6.61 (d, J=1.9 Hz, 1H), 6.59 (s, 1H), 6.53 (s,
1H), 5.29 (s, 1H), 3.85 (s, 3H) 3.84 (s, 3H), 3.80 (s, 3H), 3.7
(s, 3H), 3.77 (d, J=20.4, 1H) , 3.74 (d, J=20.4, 1H) , 2.98
(s, 3H); 13C NMR (CDCl3): d=168.5, 149.6, 148.9, 148.7,
148.0, 133.9, 126.5, 122.5, 119.2, 111.2, 109.9, 109.5, 109.2,
67.5, 56.0, 35.7, 33.3
8.2 Hz, 1H), 6.58 (dd, J=2.3, 8.2 Hz, 1H), 6.48 (d, J=2.3,
1H) 6.09 (s, 1H), 4.24–4.17 (m, 4H), 2.36 (s, 3H); 13C NMR
(CDCl3); d=166.4, 146.5, 144.7, 143.9, 143.6, 136.0, 134.4,
129.9, 129.2, 129.0, 128.8, 128.2, 128.1, 124.7, 123.7, 121.2,
117.4, 116.9, 65.3, 64.4, 64.3, 21.7; HR-MS (EI): m/z=
421.0973, calcd. for C23H19NO5S: 421.0984.
Synthesis of 23 and 24 (Scheme 3)
A flask was charged with RhACHTNUGRTENNUG(acac)ACHTUNGTRNE(NGUN C2H4)2 (0.015 mmol, 3
mol%) and N-Me-BIPAM (19, 0.0165 mmol, 3.3 mol%)
under a nitrogen atmosphere. DME (2 mL) was added and
the mixture then stirred at room temperature for 30 min.
Arylboronic acid (12n or 12o, 0.75 mmol) and aldimine (22,
0.5 mmol) were added to this catalyst solution. After being
stirred for 16 h at 808C, the product was extracted with
ethyl acetate, washed with brine and dried over MgSO4.
Chromatography on silica gel with hexane/ethyl acetate
gave the product.
To a solution of 26 (260 mg, 0.727 mmol) in THF (7 mL),
BH3·Me2S (0.7 mL, 7.27 mmol) was added under nitrogen
atmosphere. The reaction mixture was refluxed for 1 h. The
reaction mixture was cooled to room temperature, and then
the solvent and dimethyl sulfide were evaporated. After an
addition of 6N HCl (7.27 mL) to the residue, the solution
was heated at 1008C for 1 h and then cooled to room tem-
perature. The mixture was neutralized with 4N NaOH and
extracted with CH2Cl2. The organic layer was washes with
brine and dried over MgSO4. After concentration, the prod-
uct (cryptostyline II, 27) was isolated by chromatography on
basic alumina with hexane/ethyl acetate ; yield: 146 mg
23: [a]2D2: À13.98 (c 0.50, CHCl3), 98% ee (Chiralpak IB,
hexane/2-propanol=2/1, flow=1.0 mLminÀ1, wavelength=
1
230 nm, tR =18.0 and 20.6 min); H NMR (CDCl3): d=8.11
(d, J=8.6 Hz, 2H), 7.78 (d, J=9.0 Hz, 2H), 6.75–6.52 (m,
4H),6.35 (s, 1H), 6.30 (d, J=7.7 Hz, 1H), 5.78 (d, J=
7.7 Hz, 1H), 3.83 (s, 3H), 3.80 (s, 3H), 3.73 (s, 3H), 3.68 (s,
3H) ,3.56 (s, 3H) 3.49 (d, J=15.4 Hz, 1H), 3.43 (d, J=
15.4 Hz, 1H); 13C NMR (CDCl3): d=173.0, 149.6, 149.1,
148.7, 148.0, 146.6, 131.7, 130.5, 128.4, 124.7, 123.7, 119.4,
114.3, 112.1, 110.7, 110.4, 59.0, 56.1, 56.0, 55.9, 52.6, 37.9;
HR-MS (EI): m/z=560.1476, calcd. for C26H28N2O10S:
560.1465.
1
(58%); [a]23: +54.5 (c 0.26, CHCl3); H NMR (CDCl3): d=
6.82–6.97 (Dm, 2H), 6.73 (s, 1H), 6.58 (s, 1H), 6.11 (s, 1H),
4.08 (s, 1H), 3.88 (s, 3H), 3.84 (s, 3H), 3.80 (s, 3H), 3.20–
3.07 (m, 2H), 2.74–2.55 (m, 2H), 2.22 (s, 3H); 13C NMR
(CDCl3): d=149.3, 148.3, 147.4, 147.0, 136.3, 130.5, 126.4,
122.1, 111.8, 111.3, 110.6, 110.3, 71.1, 55.9, 55.8, 52.6, 44.2,
28.7; HR-MS (EI): m/z=357.1952, calcd. for C21H27NO4
[M+Me]+: 357.1940.
24: [a]2D3: À17.2 (c 0.55, CHCl3), 98% ee (Chiralcel IB
column, hexane/2-propanol=2/1, flow=1.0 mLminÀ1, wave-
length=230 nm, tR =32.4 min and 36.1 min); 1H NMR
(CDCl3): d=8.13 (d, J=8.6 Hz, 2H), 7.80 (d, J=9.1 Hz,
2H), 6.65–6.56 (m, 4H), 6.36 (s, 1H), 6.28 (d, J=7.7 Hz,
1H), 5.90 (d, J=1.3 Hz, 1H), 5.87 (d, J=1.3, 1H) 5.74 (d,
J=7.7 Hz, 1H), 3.83 (s, 3H), 3.71 (s, 3H), 3.59 (s, 3H), 3.49
(d, J=15.4 Hz, 1H) , 3.49 (d, J=15.4 Hz, 1H); 13C NMR-
ACHTUNGTRENNUNG(CDCl3): d=172.9, 149.7, 148.8, 148.1, 147.3, 146.5, 133.2,
Computational Details
130.5, 128.4, 124.6, 123.7, 120.7, 114.5, 112.1, 108.2, 107.7,
101.4, 59.1, 56.0, 55.8, 52.7, 37.9; HR-MS (EI): m/z=
544.1152, calcd. for C25H24N2O10S: 544.1152.
All calculations were performed by means of the density
functional theory method, the hybrid Becke3LYP functional
with a hybrid Becke exchange functional, and a Lee–Yang–
Parr correlation functional as implemented in Gaussian
03.[19] The LanL2DZ basis set, with relativistic effective core
potentials, was used for the Rh atoms.[20] The basis set used
for the remaining atoms was the standard 6–31G.
Synthesis of 25 (Scheme 3)
A flask was charged with 23 (459 mg, 0.82 mmol), p-methox-
ybenzenethiol (0.3 mL, 2.46 mmol), CH3CN (4.9 mL) and
DMSO (0.1 mL) in an nitrogen atmosphere. Then K2CO3
(566 mg, 4.1 mmol) was added and the mixture stirred for
16 h at 508C. The reaction mixture was extracted with
Adv. Synth. Catal. 2009, 351, 260 – 270
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269

Kazunori Kurihara et al.
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Acknowledgements
This work was supported by a Grant-in-Aid for Scientific Re-
search in Priority Areas (No. 18064001, Synergy of Elements)
and the Global COE Program (No. B01, Catalysis as the
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270
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Adv. Synth. Catal. 2009, 351, 260 – 270