Ferrocene analogues of hydrogen-bond-donor catalysts: An investigative study on asymmetric Michael addition of 1,3-dicarbonyl compounds to nitroalkenes

Article abstract of DOI:10.1055/s-0034-1379491

This report describes the synthesis of eight ferrocene derivatives of squaramide- or thiourea- based bifunctional catalysts containing cinchona alkaloid moieties. A stepwise sequential route was used to assemble the various components of these ferrocene d

Full text of DOI:10.1055/s-0034-1379491

Accounts and
Rapid Communications in
Synthetic Organic Chemistry
6
<1/(77
SUPPORTING INFORMATION
Supporting Information
for DOI: 10.1055/s-0034-1379491
Georg Thieme Verlag KG Stuttgart · New York 2014
©
Thieme

Ferrocene Analogue of H-bond donor catalyst: An Investigative Study on
Asymmetric Michael Addition of 1,3-Dicarbonyl Compounds to Nitroalkenes
Kadiyala Srinivasa Rao, Rajiv Trivedi,* M. Lakshmi Kantam
Inorganic and Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology,
Uppal Road, Tarnaka, Hyderabad, Telangana 500007, India.
*Corresponding Author. Phone: +91 40 27191667; Fax: +91 40 27160921
E-mail: trivedi@iict.res.in, rtrajiv401@gmail.com
List of Contents
1
2
3
4
5
6
. General method
. Procedure for the synthesis of catalysts 1a-j
. General Procedure for the Enantioselective Michael Addition Reactions
1
13
.
H NMR, C NMR spectra of catalysts 1k, 1l, 1a-j, products 4, 6 and 7
. HPLC spectra of product 4, 6 and 7
. References

1
) General method
All reactions were carried out an inert atmosphere unless otherwise indicated, following standard
syringe septa techniques. Chemicals were purchased from Aldrich and used as received. Solvents
used for reactions were dried before use according to standard procedures where needed. Product
purification by Flash chromatography was carried out with silica gel (60-120 mesh). Technical
grade solvents were used for chromatography and distilled prior to use. NMR spectra were
1
13
recorded in Fourier transform mode. H and C NMR spectra were recorded with Bruker-
Avance 300 MHz, Varian Inova 400 MHz, Varian Inova 400 MHz spectrometers using
1
trimethylsilane as an internal standard in CDCl and DMSO-d solvents. Multiplicities in the H
3
6
NMR spectra are described as: s = singlet, d = doublet, t = triplet, q = quartet, qt = quintet, m =
multiplet, br = broad; coupling constants are reported in Hz. IR spectra were recorded on a
-1
Thermo Nicolet Nexus 670 spectrometer and reported in cm . Mass spectra were recorded with
a Waters 2695 for low (MS) and Thermo Scientific Exactive spectrometer for HRMS. Melting
points were recorded on a Toshniwal melting point apparatus. Enantiomeric excesses were
determined by using HPLC analysis with Daicel Chiralpak OD-H or AD-H or AS-H or IC
columns, as indicated.
Scheme 1. Preparation of squaramide derived bifunctional catalysts 1a-b

Scheme 2. Preparation of squaramide derived bifunctional catalysts 1c-f
Scheme 3. Preparation of thiourea based bifunctional catalysts 1g-j

2. Procedure for the Synthesis of catalysts
2
.1. Procedure for the Synthesis of compound 1k
To a solution of dimethyl squarate (710 mg, 5 mmol) in CH Cl (10 mL) was added a solution of
2
2
benzyl amine (0.57 ml, 5.25 mmol) in CH Cl (5 mL) under N atmosphere. After 24 h, the
2
2
2
reaction was completed (monitored by TLC), then the reaction mixture was concentrated and
purified by flash chromatography (1:9 = Hexane:EtOAc) to afford 1i as a colourless solid; yield:
-1
1
0
.9 g (83%). IR (KBr, cm ): ν = 3154, 2924, 1796, 1704, 1590, 1506, 1407, 920, 740, 692; H
NMR (300 MHz, CDCl +DMSO-d ): δ = 7.40-7.24 (m, 5H), 4.73 (d, J = 6.2 Hz, 1H), 4.49 (d, J
3
6
1
3
=
6.4 Hz, 1H), 4.36 (s, 3H); C NMR (75.5 MHz, CDCl +DMSO-d ): δ = 188.6, 182.6, 176.3,
3 6
1
72.1, 137.0, 128.1, 127.1, 127.0, 59.6, 59.4, 47.5, 47.1; HRMS (ESI): m/z = 218.0809, calcd.
+
For C H NO [M+H] : 218.0811.
12
11
3
2
.2. Typical Procedure for the Preparation of Squaramide Ligands 1a-b
To a solution of 1k (1.38 mmol) in MeOH (5 mL) was added a solution of cinchona
2
alkaloid derived amine (1.52 mmol) in MeOH under an N atmosphere. After 48 h, the reaction
2
mixture was filtered. The precipitate was washed with cold MeOH (3×5 mL) to afford the
corresponding pure squaramide catalysts 1a-b as colourless solids.
30
-1
Compound 1a: yield: 530 mg (80%); [α] = -15.4 (c = 0.1 in CHCl ); IR (KBr, cm ): ν =
D
3
1
3
160, 2947, 1801, 1641, 1567, 1475, 1425, 1354, 912, 771, 726; H NMR (300 MHz,
CDCl +DMSO-d ): δ = 8.90 (d, J = 4.5 Hz, 1H), 8.51 (d, J = 8.1 Hz, 1H), 8.11 (d, J = 8.3 Hz,
3
6
1
5
2
H), 7.80-7.62 (m, 2H), 7.49 (s, 1H), 7.42 (d, J = 4.5 Hz, 1H), 7.36-7.25 (m, 5H), 6.09 (brs, 1H),
.86-5.71 (m, 1H), 5.05-4.93 (m, 2H), 4.81-4.64 (m, 2H), 3.34-3.12 (m, 3H), 2.79-2.66 (m, 2H),
.62-2.56 (m, 1H), 2.36-2.25 (m, 1H), 1.70-1.50 (m, 3H), 1.46-1.33 (m, 1H), 0.83-0.72 (m, 1H);
C NMR (75.5 MHz, CDCl +DMSO-d ): δ = 182.0, 166.5, 149.5, 147.9, 145.7, 141.0, 137.6,
1
3
3
6
1
2
29.5, 128.8, 128.2, 127.4, 127.2, 126.5, 126.1, 123.1, 113.9, 59.8, 55.5, 48.8, 47.1, 27.1, 26.8,
+
5.5; HRMS (ESI): m/z = 479.2427, calcd. For C H N O [M+H] : 479.2441.
3
0
31
4
2
3
0
-1
Compound 1b: yield: 584 mg (83%); [α] = -40.5 (c = 0.1 in CHCl ); IR (KBr, cm ): ν =
D
3
1
3
161, 2943, 1799, 1642, 1566, 1476, 1436, 1355, 1266, 1036, 730; H NMR (300 MHz,
CDCl +DMSO-d ): δ = 8.74 (d, J = 4.5 Hz, 1H), 7.99 (d, J = 9.2 Hz, 1H), 7.84 (brs, 1H), 7.55-
3
6

7.50 (m, 1H), 7.42-7.23 (m, 7H), 6.11 (brs, 1H), 5.91-5.77 (m, 1H), 5.07-4.96 (m, 2H), 4.72 (d, J
=
5.6 Hz, 2H), 4.02 (s, 3H), 3.54-3.40 (m, 1H), 3.35-3.23 (m, 2H), 2.79-2.65 (m, 2H), 2.61-2.56
13
(
m, 1H), 2.38-2.27 (m, 1H), 1.70-1.45 (m, 4H), 0.78-0.65 (m, 1H); C NMR (75.5 MHz,
CDCl +DMSO-d ): δ = 182.1, 166.9, 166.5, 157.8, 146.9, 144.1, 143.8, 141.1, 137.6, 130.9,
3
6
1
28.2, 127.5, 127.3, 121.9, 113.9, 101.0, 78.0, 59.2, 55.6, 55.4, 47.2, 27.2, 27.0, 25.9; HRMS
+
(
ESI): m/z = 509.2535, calcd. For C H N O [M+H] : 509.2547.
3
1
33
4
3
2
.3. Procedure for the Synthesis of compound 1l
To a solution of dimethyl squarate (994 mg, 7 mmol) in CH Cl (10 mL) was added a
2
2
1
solution of amino methyl ferrocene (1.51 g, 7.05 mmol) in CH Cl (3 mL) under N atmosphere.
2
2
2
After 24 h, the reaction was completed (monitored by TLC), then the reaction mixture was
concentrated and purified by flash chromatography (1:9 = Hexane:EtOAc) to afford 1l as a
-1
yellow solid; yield: 1.83 g (80%). IR (KBr, cm ): ν = 3250, 3078, 2938, 1802, 1695, 1620, 1504,
1
1
6
1
398, 1340, 1281, 1037, 820; H NMR (300 MHz, CDCl ): δ = 6.58 (brs, 1H), 4.59-4.27 (m,
3
1
3
H), 4.19 (s, 8H); C NMR (75.5 MHz, CDCl +DMSO-d ): δ = 188.5, 182.3, 176.5, 176.0,
3
6
71.4, 83.5, 83.8, 67.8, 67.6, 67.4, 59.4, 59.3, 43.2, 42.8; HRMS (ESI): m/z = 348.02908, calcd.
+
For C H NO FeNa [M+Na] : 348.02936.
16
15
3
2
.4. Typical Procedure for the Preparation of Squaramide Ligands 1c-f
To a solution of 2 (0.8 mmol) in MeOH (5 mL) was added a solution of cinchona alkaloid
2
derived amine (0.85 mmol) in MeOH under an N atmosphere. After 48 h, the reaction mixture
2
was filtered. The precipitate was washed with cold MeOH (3×5 mL) to afford the corresponding
pure squaramide catalysts 1c-f as pale yellow solids.
30
Compound 1c: yield: 390 mg (83%); m.p. 223-225°C; [α] = +46.3 (c = 0.1 in CHCl ); IR
D
3
-1
(
KBr, cm ): ν = 3200, 2944, 1797, 1644, 1575, 1466, 1330, 817, 769; elemental analysis (%): C
1
6
8
7
1
3
0
9.12, H 6.07, N 9.51; H NMR (300 MHz, CDCl +DMSO-d ): δ = 8.90 (d, J = 4.3 Hz, 1H),
3
6
.50 (d, J = 8.3 Hz, 1H), 8.11 (d, J = 8.4 Hz, 1H), 7.75 (t, J = 7.5, 7.3 Hz, 1H), 7.66 (t, J = 7.5,
.1 Hz, 1H), 7.46 (s, 2H), 7.40 (d, J = 4.3 Hz, 1H), 6.96 (brs, 1H), 6.07 (brs, 1H), 5.86-5.71 (m,
H), 5.05-4.93 (m, 2H), 4.61-4.38 (m, 2H), 4.22-4.16 (m, 2H), 4.14 (s, 5H), 3.47-3.32 (m, 2H),
.31-3.18 (m, 2H), 2.75-2.64 (m, 2H), 2.30 (brs, 1H), 1.71-1.48 (m, 3H), 1.46-1.32 (m, 3H),
1
3
.86-0.70 (m, 1H); C NMR (75.5 MHz, CDCl +DMSO-d ): δ = 183.2, 182.5, 168.0, 167.3,
3
6

1
4
5
50.1, 148.5, 141.4, 130.8, 129.8, 128.4, 127.3, 124.0, 115.2, 84.8, 69.0, 68.9, 68.5, 56.3, 44.3,
+
1.2, 39.6, 27.8, 27.7, 26.5; HRMS (ESI): m/z = 587.20972, calcd. For C H N O Fe [M+H] :
3
4
35
4
2
87.21039.
3
0
Compound 1d: yield: 410 mg (87%); m.p. 196-197°C; [α] = -18.2 (c = 0.1 in CHCl ); IR
D
3
-1
(
KBr, cm ): ν = 3260, 3076, 2933, 2867, 1636, 1533, 1458, 1337, 1285, 822, 758; elemental
1
analysis (%): C 68.97, H 6.13, N 9.31; H NMR (300 MHz, CDCl +DMSO-d ): δ = 8.89 (d, J =
3
6
4
7
5
2
0
1
6
.5 Hz, 1H), 8.45 (d, J = 8.3 Hz, 1H), 8.09 (d, J = 8.3 Hz, 1H), 7.75 (t, J = 7.7, 7.3 Hz, 1H),
.69-7.59 (m, 3H), 7.43 (d, J = 4.3 Hz, 1H), 7.08 (brs, 1H), 6.18-6.0 (m, 1H), 5.93-5.77 (m, 1H),
.23-5.07 (m, 2H), 4.58-4.40 (m, 2H), 4.23-4.17 (m, 2H), 4.14 (s, 5H), 3.23-3.11 (m, 2H), 2.97-
.86 (m, 2H), 2.34-2.20 (m, 1H), 1.65-1.60 (m, 3H), 1.35-1.21 (m, 1H), 1.17-1.05 (m, 1H), 1.03-
13
.93 (m, 1H), 0.91-0.82 (m, 1H); C NMR (75.5 MHz, CDCl +CD OD-d ): δ = 182.4, 181.7,
3
3
4
66.9, 166.6, 149.1, 147.6, 146.4, 139.2, 129.9, 128.9, 127.4, 126.4, 123.1, 114.8, 83.9, 68.2,
8.0, 67.6, 60.0, 46.1, 43.4, 38.5, 31.1, 27.0, 25.8, 25.0; HRMS (ESI): m/z = 587.20991, calcd.
+
For C H N O Fe [M+H] : 587.21039.
34
35
4
2
30
Compound 1e: yield: 414 mg (84%); m.p. 218-220°C; [α] = +25.6 (c = 0.1 in CHCl ); IR
D
3
-1
(
KBr, cm ): ν = 3327, 2927, 2851, 1626, 1576, 1440, 1312, 1243, 895, 650; elemental analysis
1
(
%): C 68.15, H 6.41, N 8.57; H NMR (300 MHz, CDCl +DMSO-d ): δ = 8.73 (d, J = 3.7 Hz,
3
6
1H), 7.96 (d, J = 8.8 Hz, 1H), 7.83 (s, 1H), 7.62-7.53 (m, 2H), 7.43-7.31 (m, 2H), 6.99 (brs, 1H),
6.24-6.08 (m, 1H), 5.94-5.78 (m, 1H), 5.25 (d, J = 17.5 Hz, 1H), 5.09 (d, J = 10.3 Hz, 1H), 4.55-
4.43 (m, 2H), 4.18 (s, 2H), 4.14 (s, 5H), 4.02 (s, 3H), 3.42-3.10 (m, 3H), 2.93-2.70 (m, 3H), 2.29
1
3
(
brs, 1H), 1.69-1.51 (m, 3H), 1.11-0.97 (m, 2H); C NMR (75.5 MHz, CDCl +DMSO-d ): δ =
3 6
1
1
6
82.5, 182.2, 166.5, 166.8, 158.1, 146.7, 144.3, 139.8, 130.9, 127.6, 126.9, 122.5, 118.1, 114.4,
00.8, 83.9, 68.2, 68.0, 59.7, 55.6, 49.3, 45.9, 43.2, 38.6, 27.1, 26.3, 25.3; HRMS (ESI): m/z =
+
17.22119, calcd. For C H N O Fe [M+H] : 617.22096.
3
5
37
4
3
30
Compound 1f: yield: 435 mg (88%); m.p. 294-296°C; [α] = -43.6 (c = 0.1 in CHCl ); IR
D
3
-1
(
KBr, cm ): ν = 3167, 2933, 1799, 1648, 1561, 1466, 1327, 1223, 818, 760; elemental analysis
1
(
%): C 68.07, H 6.27, N 8.69; H NMR (300 MHz, CDCl +DMSO-d ): δ = 8.74 (d, J = 4.5 Hz,
3
6
1H), 7.96 (s, 1H), 7.94 (s, 2H), 7.88-7.68 (m, 2H), 7.46-7.34 (m, 2H), 7.22 (brs, 1H), 6.03 (brs,
1H), 5.94-5.79 (m, 1H), 5.07-4.94 (m, 2H), 4.54-4.37 (m, 2H), 4.18 (s, 2H), 4.12 (s, 5H), 3.99 (s,
3H), 3.30-3.18 (m, 2H), 2.77-2.62 (m, 2H), 2.31 (brs, 1H), 1.68-1.44 (m, 4H), 0.76-0.63 (m, 1H);

1
3
C NMR (75.5 MHz, CDCl +CD OD-d ): δ = 182.0, 181.6, 166.7, 166.4, 158.5, 146.2, 144.5,
3
3
4
1
4
6
43.6, 139.3, 129.9, 127.7, 123.1, 114.3, 100.4, 83.8, 68.0, 67.9, 67.4, 59.5, 55.3, 48.8, 45.6,
+
3.2, 38.1, 26.8, 25.7, 25.0; HRMS (ESI): m/z = 617.22089, calcd. For C H N O Fe [M+H] :
3
5
37
4
3
17.22096.
2.5. Typical Procedure for the Preparation of Thiourea Ligands 1g-j
2
a,d, 3
To a solution of isothiocyanate
(0.7 mmol) in MeOH (5 mL) was added a solution of
amino methyl ferrocene (161 mg, 0.75 mmol) in MeOH (2 mL) under N atmosphere. After 48 h,
2
the reaction mixture was filtered. The precipitate was washed with cold MeOH (3×2 mL) to
afford the corresponding pure thiourea catalysts 1g-j as pale yellow solids.
30
Compound 1g: yield: 312 mg (81%); m.p. 119-120°C; [α] = -49.4 (c = 0.1 in CHCl ); IR
D
3
-1
(
KBr, cm ): ν = 3326, 2929, 2851, 1626, 1575, 1536, 1312, 1244, 1048, 820, 759, 646;
1
elemental analysis (%): C 66.93, H 6.05, N 9.92, S 5.53; H NMR (300 MHz, CDCl +DMSO-
3
d6): δ = 8.85 (d, J = 4.5 Hz, 1H), 8.45 (d, J = 8.3 Hz, 1H), 8.09 (d, J = 8.3 Hz, 1H), 7.72 (t, J =
8
5
2
.4, 7.3 Hz, 1H), 7.65-7.55 (m, 2H), 7.48 (s, 2H), 7.43 (d, J = 4.3 Hz, 1H), 5.98-5.82 (m, 1H),
.81-5.67 (m, 1H), 5.21-5.06 (m, 2H), 4.40-4.28 (m, 2H), 4.16-4.14 (m, 2H), 4.12 (s, 5H), 3.05-
13
.88 (m, 4H), 2.35-2.21 (m, 1H), 1.63-1.42 (m, 3H), 1.35-1.17 (m, 2H), 0.93-0.76 (m, 2H); C
NMR (75.5 MHz, CDCl +DMSO-d ): δ = 156.6, 149.2, 129.1, 128.1, 126.4, 125.6, 123.5, 114.0,
3
6
6
7.7, 67.5, 67.4, 67.1, 67.0, 60.0, 54.6, 47.3, 42.9, 40.4, 38.2, 33.0, 26.4, 24.8, 24.0; HRMS
+
(
ESI): m/z = 551.19124, calcd. For C H N FeS [M+H] : 551.19264.
3
1
35
4
30
Compound 1h: yield: 324 mg (84%); m.p. 172-173°C; [α] = +56.8 (c = 0.1 in CHCl ); IR
D
3
-1
(
KBr, cm ): ν = 3252, 3076, 2931, 2865, 1617, 1511, 1458, 1336, 1283, 1029, 821, 758;
1
elemental analysis (%): C 67.54, H 6.32, N 9.65, S 5.22; H NMR (300 MHz, CDCl +DMSO-
3
d6): δ = 8.90-8.81 (m, 1H), 8.49-8.38 (m, 1H), 8.14-8.04 (m, 1H), 7.76-7.68 (m, 1H), 7.65-7.52
(m, 2H), 7.49-7.39 (m, 3H), 5.97-5.79 (m, 1H), 5.71 (brs, 1H), 5.21-5.05 (m, 2H), 4.37-4.26 (m,
2
1
1
4
5
H), 4.14 (s, 2H), 4.12 (s, 5H), 3.05-2.86 (m, 4H), 2.33-2.21 (m, 1H), 1.65-1.38 (m, 4H), 1.31-
13
.19 (m, 1H), 0.98-0.74 (m, 2H); C NMR (75.5 MHz, CDCl +DMSO-d ): δ = 149.0, 147.3,
3
6
39.4, 128.9, 128.0, 126.5, 125.3, 123.5, 113.8, 67.6, 67.5, 67.3, 67.1, 67.0, 60.0, 48.1, 46.3,
+
2.9, 38.2, 26.5, 25.5, 24.2; HRMS (ESI): m/z = 551.19202, calcd. For C H N FeS [M+H] :
31
35
4
51.19264.

30
Compound 1i: yield: 339 mg (83%); m.p. 214-216°C; [α] = -64.5 (c = 0.1 in CHCl ); IR
D
3
-1
(
KBr, cm ): ν = 3326, 2929, 2850, 1625, 1575, 1535, 1438, 1312, 1244, 1088, 893, 646;
1
elemental analysis (%): C 66.49, H 6.60, N 9.38, S 4.98; H NMR (300 MHz, CDCl +DMSO-
3
d6): δ = 8.71 (d, J = 4.1 Hz, 1H), 8.16 (brs, 1H), 8.0-7.88 (m, 2H), 7.61 (s, 1H), 7.50-7.27 (m,
3H), 6.11 (brs, 1H), 5.81-5.66 (m, 1H), 5.07-4.93 (m, 2H), 4.42-4.26 (m, 2H), 4.15 (s, 2H), 4.12
(s, 5H), 4.02 (s, 3H), 3.44-3.23 (m, 3H), 2.89-2.77 (m, 2H), 2.46-2.31 (m, 1H), 1.76-1.58 (m,
1
3
3
1
5
5
H), 1.41-1.26 (m, 1H), 1.16-0.91 (m, 2H); C NMR (75.5 MHz, CDCl +DMSO-d ): δ = 156.8,
3 6
46.6, 143.7, 139.3, 130.4, 127.3, 120.9, 119.4, 114.2, 102.0, 83.6, 67.6, 67.4, 67.3, 66.9, 59.5,
4.9, 54.4, 47.3, 42.9, 40.7, 37.7, 32.9, 26.3, 25.9, 24.7, 24.4, 23.9; HRMS (ESI): m/z =
+
81.20306, calcd. For C H N OFeS [M+H] : 581.20320.
3
2
37
4
3
0
Compound 1j: yield: 352 mg (86%); m.p. 128-129°C; [α] = +34.3 (c = 0.1 in CHCl ); IR
D
3
-1
(
KBr, cm ): ν = 3324, 3073, 2929, 2854, 1623, 1537, 1509, 1472, 1341, 1227, 1028, 825, 672;
1
elemental analysis (%): C 66.18, H 6.21, N 9.47, S 5.16; H NMR (300 MHz, CDCl +DMSO-
3
d6): δ = 8.74 (d, J = 4.5 Hz, 1H), 8.04 (d, J = 9.2 Hz, 1H), 7.72-7.56 (m, 2H), 7.40 (q, J = 9.0, 2.8
Hz, 2H), 5.75-5.60 (m, 2H), 5.06-4.98 (m, 2H), 4.37-4.21 (m, 3H), 4.11 (s, 5H), 3.97 (s, 3H),
3
1
1
5
5
.53-3.34 (m, 3H), 2.90-2.66 (m, 3H), 2.07-1.85 (m, 2H), 1.76-1.65 (m, 3H), 1.44-1.26 (m, 2H),
13
.17-1.07 (m, 1H), 0.99-0.85 (m, 1H); C NMR (75.5 MHz, CDCl +DMSO-d ): δ = 157.0,
3
6
46.7, 143.8, 139.4, 130.5, 127.5, 121.1, 119.6, 114.4, 102.0, 83.6, 67.8, 67.6, 67.5, 67.1, 59.7,
5.1, 54.5, 47.5, 43.2, 40.8, 37.9, 33.1, 26.4, 26.1, 24.9, 24.5, 24.1; HRMS (ESI): m/z =
+
81.20359, calcd. For C H N OFeS [M+H] : 581.20320.
3
2
37
4
3) General Procedure for the Enantioselective Michael Addition Reactions
To a solution of nitroolefin (0.33 mmol) in CH Cl (1.5 ml) was added bifunctional catalyst 1f (2
2
2
mg, 0.0033 mmol, 1 mol %) and the mixture was stirred for 5 min under N atmosphere. Then
2
1,3-dicarbonyl compound (0.4 mmol) was added to the mixture. Upon consumption of
nitroolefin substrate (monitored by TLC), the reaction mixture was concentrated and purified by
column chromatography to afford the conjugate addition products 4, 6 and 7.
-1
Compound 4a: white solid (93%); IR (KBr, cm ): ν = 1732, 1703, 1550, 1496, 1433, 1361,
1
1
272, 1140, 702; H NMR (300 MHz, CDCl ): δ = 7.35-7.28 (m, 3H), 7.19 (d, J = 7.72 Hz, 2H),
3
1
3
4
.68-4.59 (m, 2H), 4.37 (d, J = 11.0 Hz, 1H), 4.28-4.20 (m, 1H), 2.29 (s, 3H), 1.94 (s, 3H); C

NMR (75.5 MHz, CDCl ): δ = 201.7, 200.9, 135.9, 129.3, 128.5, 127.8, 78.1, 70.6, 42.7, 30.4,
3
+
2
9.5; HRMS (ESI): m/z = 272.08845, calcd. For C H NO Na [M+Na] : 272.08933; HPLC
13
15
4
(AD-H, 10% iPrOH in Hexanes, 1 mL/min, 210 nm): tmajor = 7.0 min, tminor = 9.4 min, 98% ee.
Configuration assignment: The absolute configuration of the product (S) was determined by
4
a
comparison of the HPLC retention time with the literature data.
-1
Compound 4b: white solid (87%); IR (KBr, cm ): ν = 1731, 1702, 1548, 1430, 1362, 1267,
1
1
140, 813; H NMR (300 MHz, CDCl ): δ = 7.13 (d, J = 7.9 Hz, 2H), 7.06 (d, J = 8.1 Hz, 2H),
3
4.64-4.57 (m, 2H), 4.36 (d, J = 10.9 Hz, 1H), 4.26-4.14 (m, 1H), 2.3 (s, 3H), 2.29 (s, 3H), 1.94
13
(
s, 3H); C NMR (75.5 MHz, CDCl ): δ = 201.8, 201.0, 138.3, 132.7, 129.9, 127.7, 78.3, 70.7,
3
+
4
2
1
2.4, 30.3, 29.4, 21.0; HRMS (ESI): m/z = 286.10501, calcd. For C H NO Na [M+Na] :
1
4
17
4
86.10498; HPLC (AD-H, 10% iPrOH in Hexanes, 1 mL/min, 210 nm): tmajor = 6.4 min, tminor
0.3 min, 96% ee.
=
Configuration assignment: The absolute configuration of the product (S) was determined by
4
b
comparison of the HPLC retention time with the literature data.
-1
Compound 4c: white solid (89%); IR (KBr, cm ): ν 1733, 1705, 1614, 1549, 1515, 1438, 1363,
1
1
8
261, 1171, 1141, 812; H NMR (300 MHz, CDCl ): δ = 7.10 (d, J = 9.0 Hz, 2H), 6.85 (d, J =
3
.3 Hz, 2H), 4.63-4.56 (m, 2H), 4.34 (d, J = 11.3 Hz, 1H), 4.24-4.11 (m, 1H), 3.78 (s, 3H), 2.30
13
(
s, 3H), 1.95 (s, 3H); C NMR (75.5 MHz, CDCl ): δ = 201.8, 201.1, 159.4, 129.0, 127.5, 114.6,
3
7
8.4, 70.8, 55.1, 42.0, 30.3, 29.4; HRMS (ESI): m/z = 302.09894, calcd. For C H NO Na
1
4
17
5
+
[
M+Na] : 302.09989; HPLC (AD-H, 10% iPrOH in Hexanes, 1 mL/min, 210 nm): t
= 9.4
major
min, tminor = 14.4 min, 92% ee.
Configuration assignment: The absolute configuration of the product (S) was determined by
4
c
comparison of the HPLC retention time with the literature data.
-1
Compound 4d: white solid (92%); IR (KBr, cm ): ν = 1732, 1703, 1600, 1554, 1543, 1495,
1
1
6
2
437, 1361, 1262, 1141, 1040, 793, 704; H NMR (300 MHz, CDCl ): δ = 7.28-7.22 (m, 1H),
3
.83-6.70 (m, 3H), 4.66-4.58 (m, 2H), 4.37 (d, J = 10.8 Hz, 1H), 4.24-4.18 (m, 1H), 3.78 (s, 3H),
1
3
.29 (s, 3H), 1.97 (s, 3H); C NMR (75.5 MHz, CDCl ): δ = 201.7, 200.9, 160.0, 137.5, 130.3,
3

+
1
19.8, 114.1, 113.5, 78.1, 70.5, 55.2, 42.7, 30.4, 29.5; MS (ESI): m/z = 302 [M+Na] ; HPLC
(
IC, 20% iPrOH in Hexanes, 1 mL/min, 254 nm): tmajor = 14.5 min, tminor = 16.3 min, >92% ee.
Configuration assignment: The absolute configuration of the product (S) was determined by
4
d
comparison of the HPLC retention time with the literature data.
-1
Compound 4e: white solid (92%); IR (KBr, cm ): ν = 1727, 1702, 1596, 1552, 1494, 1359,
1
1
6
247, 1159, 1024, 758; H NMR (300 MHz, CDCl ): δ = 7.31-7.23 (m, 1H), 7.12-7.03 (m, 1H),
3
.96-6.84 (m, 2H), 4.79 (dd, J = 12.0, 4.3 Hz, 1H), 4.65-4.54 (m, 2H), 4.54-4.43 (m, 1H), 3.88
1
3
(
s, 3H), 2.28 (s, 3H), 1.94 (s, 3H); C NMR (75.5 MHz, CDCl ): δ = 202.2, 201.5, 156.9, 130.1,
3
1
29.6, 123.3, 121.0, 111.1, 76.4, 68.8, 55.3, 38.9, 30.3, 28.7; HRMS (ESI): m/z = 302.09901,
+
calcd. For C H NO Na [M+Na] : 302.09989; HPLC (OD-H, 15% iPrOH in Hexanes, 0.5
1
4
17
5
mL/min, 230 nm): tmajor = 24.8 min, tminor = 26.9 min, >99% ee.
Configuration assignment: The absolute configuration of the product (S) was determined by
4
d
comparison of the HPLC retention time with the literature data.
-1
Compound 4f: white solid (89%); IR (KBr, cm ): ν = 1733, 1704, 1550, 1513, 1437, 1363,
1
1
267, 1141, 827; H NMR (300 MHz, CDCl ): δ = 7.21-7.14 (m, 2H), 7.08-6.98 (m, 2H), 4.60
3
1
3
(
d, J = 7.16 Hz, 2H), 4.32 (d, J = 11.9 Hz, 1H), 4.28-4.20 (m, 1H), 2.29 (s, 3H), 1.96 (s, 3H); C
NMR (75.5 MHz, CDCl ): δ = 201.4, 200.6, 164.1, 160.8, 131.7, 129.7, 129.6, 116.4, 116.2,
3
7
8.1, 70.7, 42.0, 30.3, 29.5; HRMS (ESI): m/z = 290.08008, calcd. For C H FNO Na
1
3
14
4
+
[
M+Na] : 290.07991; HPLC (OD-H, 15% iPrOH in Hexanes, 1 mL/min, 210 nm): t
= 18.7
major
min, tminor = 21.2 min, 95% ee.
Configuration assignment: The absolute configuration of the product (S) was determined by
4
d
comparison of the HPLC retention time with the literature data.
-1
Compound 4g: white solid (92%); IR (KBr, cm ): ν = 1732, 1701, 1549, 1482, 1332, 1361,
1
1
2
3
7
270, 1141, 821; H NMR (300 MHz, CDCl ): δ = 7.32 (d, J = 8.3 Hz, 2H), 7.14 (d, J = 8.3 Hz,
3
H), 4.61 (d, J = 6.79 Hz, 2H), 4.34 (d, J = 10.5 Hz, 1H), 4.29-4.16 (m, 1H), 2.3 (s, 3H), 1.98 (s,
1
3
H); C NMR (75.5 MHz, CDCl ): δ = 201.3, 200.5, 134.6, 134.5, 134.4, 129.5, 129.2, 77.8,
3
+
0.4, 42.0, 30.4, 29.6; HRMS (ESI): m/z = 306.05038, calcd. For C H ClNO Na [M+Na] :
1
3
14
4

3
06.05036; HPLC (AD-H, 20% iPrOH in Hexanes, 1 mL/min, 210 nm): tmajor = 5.5 min, tminor
3.2 min, 86% ee.
=
1
Configuration assignment: The absolute configuration of the product (S) was determined by
4
c
comparison of the HPLC retention time with the literature data.
-1
Compound 4h: white solid (90%); IR (KBr, cm ): ν = 1729, 1699, 1547, 1490, 1431, 1362,
1
1
2
3
4
3
264, 1140, 818; H NMR (300 MHz, CDCl ): δ = 7.47 (d, J = 8.3 Hz, 2H), 7.07 (d, J = 8.4 Hz,
3
H), 4.61 (d, J = 7.1 Hz, 2H), 4.33 (d, J = 10.7 Hz, 1H), 4.28-4.16 (m, 1H), 2.3 (s, 3H), 1.98 (s,
H); 13C NMR (75.5 MHz, CDCl ): δ = 201.3, 200.5, 135.0, 132.4, 129.5, 122.6, 77.8, 70.3,
3
+
2.1, 30.4, 29.6; HRMS (ESI): m/z = 349.99986, calcd. For C H BrNO Na [M+Na] :
13
14
4
49.99984; HPLC (OD-H, 10% iPrOH in Hexanes, 0.8 mL/min, 210 nm): tmajor = 39.4min, tminor
44.1 min, 97% ee.
=
Configuration assignment: The absolute configuration of the product (S) was determined by
4
b
comparison of the HPLC retention time with the literature data.
-
1
Compound 4i: white solid (91%); IR (KBr, cm ): ν = 1728, 1702, 1598, 1549, 1435, 1384,
1
1
1
3
1
367, 1256, 1142, 791, 700; H NMR (300 MHz, CDCl ): δ = 7.30-7.26 (m, 2H), 7.21-7.19 (m,
3
H), 7.10-7.06 (m, 1H), 4.67-4.59 (m, 2H), 4.35 (d, J = 10.6 Hz, 1H), 4.26-4.20 (m, 1H), 2.30 (s,
1
3
H), 2.00 (s, 3H); C NMR (75.5 MHz, CDCl ): δ = 201.3, 200.4, 138.1, 135.1, 130.5, 128.8,
3
+
28.1, 126.0, 77.7, 70.3, 42.3, 30.5, 29.7; MS (ESI): m/z = 306 [M+Na] ; HPLC (IC, 20%
iPrOH in Hexanes, 1 mL/min, 210 nm): tmajor = 7.8 min, tminor = 10.9 min, 90% ee.
Configuration assignment: The absolute configuration of the product (S) was determined by
4
d
comparison of the HPLC retention time with the literature data.
-1
Compound 4j: white solid (95%); IR (KBr, cm ): ν = 1727, 1703, 1550, 1477, 1433, 1383,
1
1
1
1
2
367, 1252, 1141, 790, 699; H NMR (300 MHz, CDCl ): δ = 7.45-7.42 (m, 1H), 7.38-7.35 (m,
3
H), 7.21 (t, J = 7.9, 7.7 Hz, 1H), 7.15-7.11 (m, 1H), 4.67-4.59 (m, 2H), 4.34 (d, J = 10.6 Hz,
1
3
H), 4.24-4.19 (m, 1H), 2.30 (s, 3H), 2.01 (s, 3H); C NMR (75.5 MHz, CDCl ): δ = 201.2,
3
00.4, 138.4, 131.7, 130.9, 130.8, 126.5, 123.2, 77.6, 70.2, 42.2, 30.4, 29.8; MS (ESI): m/z = 350
+
[
M+Na] ; HPLC (IC, 20% iPrOH in Hexanes, 1 mL/min, 210 nm): t
= 8.1 min, tminor = 11.4
major
min, 98% ee.

Configuration assignment: The absolute configuration of the product (S) was determined by
4
b
comparison of the HPLC retention time with the literature data.
-1
Compound 4k: white solid (92%); IR (KBr, cm ): ν = 1730, 1704, 1554, 1494, 1426, 1361,
1
1
1
2
1
267, 1234, 1178, 1144, 767; H NMR (300 MHz, CDCl ): δ = 7.33-7.26 (m, 1H), 7.22-7.14 (m,
3
H), 7.13-7.04 (m, 2H), 4.76-4.69 (m, 1H), 4.67-4.60 (m, 1H), 4.52-4.44 (m, 2H), 2.29 (s, 3H),
1
3
.01 (s, 3H); C NMR (75.5 MHz, CDCl ): δ = 201.3, 200.7, 161.6, 159.6, 130.5, 130.43,
3
30.40, 130.3, 125.0, 124.9, 122.8, 122.7, 116.3, 116.1, 76.5, 68.9, 37.8, 30.3, 29.2; HRMS
+
(
ESI): m/z = 290.07960, calcd. For C H FNO Na [M+Na] : 290.07991; HPLC (AD-H, 10%
1
3
14
4
iPrOH in Hexanes, 1 mL/min, 210 nm): tmajor = 14.1 min, tminor = 17.8 min, 98% ee.
Configuration assignment: The absolute configuration of the product (S) was determined by
4
b
comparison of the HPLC retention time with the literature data.
-
1
Compound 4l: white solid (90%); IR (KBr, cm ): ν = 1734, 1706, 1552, 1479, 1435, 1359,
1
1
7
260, 1170, 1137, 768; H NMR (300 MHz, CDCl ): δ = 7.47-7.41 (m, 1H), 7.29-7.22 (m, 2H),
3
.20-7.13 (m, 1H), 4.89-4.81 (m, 1H), 4.79-4.71 (m, 1H), 4.70-4.58 (m, 2H), 2.30 (s, 3H), 2.04
13
(
s, 3H); C NMR (75.5 MHz, CDCl ): δ = 201.8, 200.8, 133.7, 133.3, 130.6, 129.6, 128.9,
3
+
1
27.6, 76.1, 68.9, 38.8, 30.8, 28.4; ESI-MS: m/z = 306 (M+Na) ; HPLC (AD-H, 10% iPrOH in
Hexanes, 1 mL/min, 210 nm): tmajor = 12.6 min, tminor = 19.8 min, 88% ee.
Configuration assignment: The absolute configuration of the product (S) was determined by
4
e
comparison of the HPLC retention time with the literature data.
-1
Compound 4m: white solid (95%); IR (KBr, cm ): ν = 1727, 1702, 1553, 1472, 1433, 1359,
1
1
7
3
7
259, 1154, 762; H NMR (300 MHz, CDCl ): δ = 7.67-7.59 (m, 1H), 7.32-7.26 (m, 1H), 7.22-
3
.12 (m, 2H), 4.88-4.80 (m, 1H), 4.79-4.67 (m, 2H), 4.67-4.58 (m, 1H), 2.29 (s, 3H), 2.05 (s,
1
3
H); C NMR (75.5 MHz, CDCl ): δ = 201.9, 200.8, 135.0, 133.9, 129.9, 128.8, 128.2, 124.5,
3
+
6.2, 69.0, 41.0, 30.9, 28.3; ESI-MS: m/z = 350 (M+Na) ; HPLC (AD-H, 10% iPrOH in
Hexanes, 1 mL/min, 210 nm): tmajor = 12.9 min, tminor = 22.3 min, 99% ee.
Configuration assignment: The absolute configuration of the product (S) was determined by
4
b
comparison of the HPLC retention time with the literature data.

-1
Compound 4n: white solid (83%); IR (KBr, cm ): ν 1732, 1707, 1554, 1526, 1435, 1357, 1239,
1
1
141, 953, 854; H NMR (300 MHz, CDCl ): δ = 7.94 (d, J = 7.9 Hz, 1H), 7.59 (t, J = 7.9, 6.9
3
Hz, 1H), 7.49 (t, J = 7.9, 6.9 Hz, 1H), 7.36 (d, J = 6.9 Hz, 1H), 4.98 (dd, J = 13.9, 6.9 Hz, 1H),
4
3
7
.84 (dd, J = 12.9, 2.9 Hz, 1H), 4.77-4.71 (m, 1H), 4.68 (d, J = 8.9 Hz, 1H), 2.31 (s, 3H), 2.14 (s,
1
3
H); C NMR (75.5 MHz, CDCl ): δ = 201.5, 200.5, 149.7, 133.4, 131.1, 129.3, 129.1, 125.5,
3
6.5, 69.0, 37.0, 31.2, 30.8, 29.2; HRMS (ESI): m/z = 317.07428, calcd. For C H N O Na
1
3
14
2
6
+
[
M+Na] : 317.07441; HPLC (OD-H, 10% iPrOH in Hexanes, 1 mL/min, 210 nm): t
= 12.8
major
min, tminor = 13.7 min, 91% ee.
Configuration assignment: The absolute configuration of the product (S) was determined by
4
b
comparison of the HPLC retention time with the literature data.
-1
Compound 4o: white solid (85%); IR (KBr, cm ): ν = 1731, 1702, 1548, 1435, 1362, 1257,
1
1
1
1
2
136, 950, 821, 747; H NMR (300 MHz, CDCl ): δ = 7.86-7.77 (m, 3H), 7.65 (d, J = 1.2 Hz,
3
H), 7.52-7.47 (m, 2H), 7.30 (dd, J = 8.3, 1.5 Hz, 1H), 4.80-4.65 (m, 2H), 4.50 (d, J = 10.5 Hz,
1
3
H), 4.47-4.37 (m, 1H), 2.33 (s, 3H), 1.95 (s, 3H); C NMR (75.5 MHz, CDCl ): δ = 201.7,
3
00.9, 133.2, 132.9, 129.3, 127.8, 127.6, 127.4, 126.6, 126.5, 124.9, 78.0, 70.6, 42.8, 30.4, 29.5;
+
HRMS (ESI): m/z = 322.10491, calcd. For C H NO Na [M+Na] : 322.10498; HPLC (AD-H,
1
7
17
4
10% iPrOH in Hexanes, 1 mL/min, 210 nm): tmajor = 9.9 min, tminor = 12.5 min, 88% ee.
Configuration assignment: The absolute configuration of the product (S) was determined by
4
e
comparison of the HPLC retention time with the literature data.
-1
Compound 4p: white solid (93%); IR (KBr, cm ): ν = 1729, 1698, 1554, 1503, 1440, 1363,
1
1
3
3
7
2
8
262, 1207, 1144, 754; H NMR (300 MHz, CDCl ): δ = 7.36 (d, J = 1.5 Hz, 1H), 6.30 (dd, J =
3
.0, 2.2 Hz, 1H), 6.18 (d, J = 3.0 Hz, 1H), 4.67 (d, J = 4.5 Hz, 2H), 4.43-4.30 (m, 2H), 2.29 (s,
1
3
H), 2.09 (s, 3H); C NMR (75.5 MHz, CDCl ): δ = 201.4, 200.7, 149.4, 142.8, 110.8, 108.8,
3
+
5.8, 67.9, 36.5, 30.5, 29.2; HRMS (ESI): m/z = 262.06839, calcd. For C H NO Na [M+Na] :
1
1
13
5
62.06859; HPLC (AD-H, 10% iPrOH in Hexanes, 1 mL/min, 210 nm): tmajor = 7.2 min, tminor
.5 min, 95% ee.
=
Configuration assignment: The absolute configuration of the product (S) was determined by
4
b
comparison of the HPLC retention time with the literature data.

-1
Compound 4q: white solid (94%); IR (KBr, cm ): ν = 1726, 1696, 1551, 1435, 1359, 1246,
1
1
4
209, 1141, 714; H NMR (300 MHz, CDCl ): δ = 7.21-7.15 (m, 1H), 6.89-6.80 (m, 2H), 4.62-
3
1
3
.57 (m, 2H), 4.52-4.43 (m, 1H), 4.34 (d, J = 10.0 Hz, 1H), 2.23 (s, 3H), 2.01 (s, 3H); C NMR
(
75.5 MHz, CDCl ): δ = 201.4, 200.6, 138.6, 127.3, 126.9, 125.6, 78.4, 70.8, 38.1, 30.5, 29.6;
3
+
HRMS (ESI): m/z = 278.04568, calcd. For C H SNO Na [M+Na] : 278.04575; HPLC (AS-H,
11
13
4
10% iPrOH in Hexanes, 0.6 mL/min, 230 nm): tmajor = 37.1 min, tminor = 47.4 min, 94% ee.
Configuration assignment: The absolute configuration of the product (S) was determined by
4
e
comparison of the HPLC retention time with the literature data.
Compound 4r: white solid (91%); IR (KBr, cm-1): ν = 1731, 1703, 1553, 1491, 1443, 1363,
1
1
6
2
1
3
237, 1172, 1142, 1037, 931, 820; H NMR (300 MHz, CDCl ): δ = 6.74 (d, J = 7.9 Hz, 1H),
3
.68-6.63 (m, 2H), 5.95 (s, 2H), 4.60-4.56 (m, 2H), 4.31 (d, J = 10.8 Hz, 1H), 4.20-4.09 (m, 1H),
1
3
.29 (s, 3H), 1.99 (s, 3H); C NMR (75.5 MHz, CDCl ): δ = 201.6, 200.8, 148.2, 147.6, 129.3,
3
21.4, 108.7, 108.0, 101.3, 78.3, 70.7, 60.3, 42.4, 30.3, 29.4, 25.2; HRMS (ESI): m/z =
+
16.07880, calcd. For C H NO Na [M+Na] : 316.07916; HPLC (AD-H, 10% iPrOH in
14
15
6
Hexanes, 1 mL/min, 210 nm): tmajor = 28.2 min, tminor = 34.3 min, 96% ee.
Configuration assignment: The absolute configuration of the product (S) was determined by
4
f
comparison of the HPLC retention time with the literature data.
-1
Compound 6a: white solid (80%); IR (KBr, cm ): ν = 1736, 1555, 1496, 1435, 1378, 1258,
1
1
157, 701; H NMR (300 MHz, CDCl ): δ = 7.35-7.21 (m, 5H), 4.98-4.84 (m, 2H), 4.25 (td, J =
3
1
3
9
.0, 6.0 Hz, 1H), 3.87 (d, J = 9.0 Hz, 1H), 3.76 (s, 3H), 3.56 (s, 3H); C NMR (75.5 MHz,
CDCl ): δ = 167.7, 167.1, 136.1, 128.9, 128.3, 127.8, 77.3, 54.7, 52.9, 52.7, 42.9, 31.5, 22.6;
3
+
HRMS (ESI): m/z = 304.07874, calcd. For C H NO Na [M+Na] : 304.07916; HPLC (AD-H,
1
3
15
6
10% iPrOH in Hexanes, 1 mL/min, 210 nm): tmajor = 17.7 min, tminor = 10.7 min, 33% ee.
Configuration assignment: The absolute configuration of the product (S) was determined by
4
a
comparison of the HPLC retention time with the literature data.
-1
Compound 6b: colourless oil (93%); IR (Neat, cm ): ν = 1732, 1555, 1498, 1451, 1373, 1255,
1
1
179, 1027, 701; H NMR (300 MHz, CDCl ): δ = 7.35-7.22 (m, 5H), 4.98-4.81 (m, 2H), 4.29-
3
4.17 (m, 3H), 4.0 (q, J = 13.5, 6.7 Hz, 2H), 3.82 (d, J = 9.0 Hz, 1H), 1.26 (t, J = 7.5, 6.7 Hz, 3H),

1
3
1
.04 (t, J = 7.5, 6.7 Hz, 3H); C NMR (75.5 MHz, CDCl ): δ = 167.4, 166.7, 136.2, 128.8,
3
1
28.2, 127.9, 77.6, 62.0, 61.8, 54.9, 42.9, 13.9, 13.6; HRMS (ESI): m/z = 332.11028, calcd. For
+
C H NO Na [M+Na] : 332.11046; HPLC (AD-H, 10% iPrOH in Hexanes, 1 mL/min, 210
15
19
6
nm): tmajor = 21.6 min, tminor = 8.1 min, 90% ee.
Configuration assignment: The absolute configuration of the product (S) was determined by
4
a
comparison of the HPLC retention time with the literature data.
-1
Compound 6c: white solid (89%); IR (KBr, cm ): ν = 1680, 1592, 1548, 1447, 1380, 1343,
1
1
2
268, 1194, 969, 761, 684; H NMR (300 MHz, CDCl ): δ = 7.89-7.85 (m, 2H), 7.80-7.76 (m,
3
H), 7.56-7.49 (m, 2H), 7.41-7.34 (m, 4H), 7.25-7.14 (m, 5H), 5.84 (d, J = 7.9 Hz, 1H), 4.99 (d,
1
3
J = 6.7 Hz, 2H), 4.62 (q, J = 14.6, 6.8 Hz, 1H); C NMR (75.5 MHz, CDCl ): δ = 194.1, 193.5,
3
1
36.7, 136.1, 135.7, 134.0, 133.7, 128.9, 128.8, 128.7, 128.5, 128.2, 128.1, 77.2, 59.7, 43.9;
+
HRMS (ESI): m/z = 396.12028, calcd. For C H NO Na [M+Na] : 396.12063; HPLC (AD-H,
2
3
19
4
25% iPrOH in Hexanes, 1 mL/min, 210 nm): tmajor = 9.7 min, tminor = 21.5 min, 90% ee.
Configuration assignment: The absolute configuration of the product (S) was determined by
4
b
comparison of the HPLC retention time with the literature data.
-1
Compound 6d: white solid (84%); IR (KBr, cm ): ν = 1715, 1673, 1542, 1496, 1449, 1376,
1
1
7
4
280, 1165, 761, 699; H NMR (300 MHz, CDCl ): δ = 8.02 (d, J = 7.5 Hz, 1.3H), 7.82 (d, J =
3
.5 Hz, 0.7H), 7.67-7.39 (m, 3H), 7.36-7.11 (m, 5H), 5.23-5.15 (m, 1H), 4.90-4.61 (m, 2H),
13
.58-4.49 (m, 0.7H), 4.47-4.38 (m, 0.3H), 2.22 (s, 1H), 1.94 (s, 2H); C NMR (75.5 MHz,
CDCl ): δ = 201.5, 200.7, 193.9, 193.6, 136.4, 136.1, 136.0, 135.9, 134.3, 133.9, 129.1, 128.9,
3
1
2
28.8, 128.8, 128.4, 128.3, 128.0, 127.9, 127.9, 78.0, 77.9, 65.1, 64.5, 43.3, 43.2, 29.6, 28.5,
+
2.5, 14.1, 14.0 ; HRMS (ESI): m/z = 312.12269, calcd. For C H NO [M+H] : 312.12303;
1
8
18
4
HPLC (AD-H, 2% iPrOH in Hexanes, 1.0 mL/min, 210 nm): major diastereomer: tmajor = 28.0
min, tminor = 37.5 min, 88% ee, minor diastereomer: tmajor = 22.8 min, tminor = 34.0 min, 88% ee.
Configuration assignment: The absolute configuration of the product (S) was determined by
4
b
comparison of the HPLC retention time with the literature data.
-1
Compound 6e: white solid (90%); IR (KBr, cm ): ν = 1742, 1533, 1497, 1431, 1360, 1250,
1
1
146, 702; H NMR (300 MHz, CDCl ): δ = 7.35-7.27 (m, 3H), 7.24-7.17 (m, 2H), 4.86-4.80
3

(m, 1H), 4.78 (d, J = 6.7 Hz, 1H), 4.79-4.76 (m, 1H), 4.29-4.18 (m, 1H), 4.14 (d, J = 9.8 Hz,
0.5H), 4.05 (d, J = 9.8 Hz, 0.5H), 3.78 (s, 1.5H), 3.53 (s, 1.5H), 2.30 (s, 1.5H), 2.05 (s, 1.5H);
1
3
C NMR (75.5 MHz, CDCl ): δ = 201.0, 200.2, 167.9, 167.3, 136.3, 136.1, 129.1, 128.9, 128.3,
3
1
28.2, 127.8, 127.7, 77.7, 77.5, 61.7, 61.3, 52.9, 52.7, 42.5, 42.2, 30.3, 30.2; HRMS (ESI): m/z =
+
2
88.08386, calcd. For C H NO Na [M+Na] : 288.08424; HPLC (AD-H, 5% iPrOH in
13
15
5
Hexanes, 1 mL/min, 210 nm): major diastereomer: tmajor = 9.4 min, tminor = 13.7 min, 90% ee,
minor diastereomer: tmajor = 16.7 min, tminor = 12.9 min, 92% ee.
Configuration assignment: The absolute configuration of the product (S) was determined by
4
a
comparison of the HPLC retention time with the literature data.
-1
Compound 6f: colourless oil (87%); IR (Neat, cm ): ν = 1739, 1718, 1554, 1496, 1432, 1375,
1
1
4
248, 1180, 1019, 702; H NMR (300 MHz, CDCl ): δ = 7.37-7.25 (m, 3H), 7.23-7.17 (m, 2H),
3
.86-4.72 (m, 2H), 4.28-4.16 (m, 2H), 4.12 (d, J = 9.8 Hz, 0.6H), 4.03 (d, J = 9.8 Hz, 0.4H), 3.96
(q, J = 14.3, 7.5 Hz, 1H), 2.30 (s, 1.6H), 2.06 (s, 1.4H), 1.28 (t, J = 6.7 Hz, 3H), 1.0 (t, J = 6.7
1
3
Hz, 1.6H); C NMR (75.5 MHz, CDCl ): δ = 201.0, 200.2, 167.3, 166.7, 136.2, 128.9, 128.7,
3
1
28.2, 128.1, 127.8, 127.7, 77.7, 77.6, 62.0, 61.8, 61.7, 61.4, 42.4, 42.1, 30.1, 29.9, 13.8, 13.5;
+
HRMS (ESI): m/z = 302.09979, calcd. For C H NO Na [M+Na] : 302.09989; HPLC (AD-H,
1
4
17
5
5% iPrOH in Hexanes, 0.8 mL/min, 210 nm): major diastereomer: tmajor = 28.2 min, tminor = 14.8
min, 85% ee, minor diastereomer: tmajor = 10.1 min, tminor = 16.0 min, 78% ee.
Configuration assignment: The absolute configuration of the product (S) was determined by
4
a
comparison of the HPLC retention time with the literature data.
-1
Compound 6g: white solid (89%); IR (KBr, cm ): ν = 1738, 1712, 1550, 1496, 1458, 1368,
1
1
4
9
252, 1138, 702; H NMR (300 MHz, CDCl ): δ = 7.38-7.27 (m, 3H), 7.24-7.18 (m, 2H), 4.87-
3
.80 (m, 0.6H), 4.78-4.64 (m, 1.6H), 4.23-4.09 (m, 1H), 4.02 (d, J = 10.3 Hz, 0.7H), 3.92 (d, J =
1
3
.6 Hz, 0.3H), 2.30 (s, 2H), 2.06 (s, 1H), 1.47 (s, 2.5H), 1.17 (s, 6.5H); C NMR (75.5 MHz,
CDCl ): δ = 201.3, 200.5, 166.6, 165.8, 136.6, 129.0, 128.7, 128.2, 127.9, 83.4, 82.9, 78.3, 77.8,
3
6
3.0, 62.7, 42.5, 42.3, 30.0, 29.6, 27.8, 27.3; HRMS (ESI): m/z = 308.14914, calcd. For
+
C H NO [M+H] : 308.14925; HPLC (AD-H, 5% iPrOH in Hexanes, 1.0 mL/min, 210 nm):
16
22
5
major diastereomer: tmajor = 5.6 min, tminor = 8.3 min, 92% ee, minor diastereomer: tmajor = 14.5
min, tminor = 10.6 min, 91% ee.

Configuration assignment: The absolute configuration of the product (S) was determined by
4
a
comparison of the HPLC retention time with the literature data.
-1
Compound 6h: white solid (93%); IR (KBr, cm ): ν = 1714, 1674, 1542, 1424, 1375, 1280,
1
1
1
1
1
4
3
167, 760, 695; H NMR (300 MHz, CDCl ): δ = 7.39-7.08 (m, 10H), 5.20 (s, 0.8H), 4.93 (s,
3
.2H), 4.81-4.71 (m, 2H), 4.29-4.15 (m, 1.6H), 4.05 (d, J = 9.0 Hz, 0.4H), 2.25 (s, 1.8H), 2.00 (s,
1
3
.2H); C NMR (75.5 MHz, CDCl ): δ = 200.8, 199.9, 167.3, 166.7, 136.2, 134.6, 134.4, 129.1,
3
28.9, 128.7, 128.6, 128.5, 128.4, 128.3, 128.2, 127.8, 127.7, 77.7, 77.5, 67.8, 67.6, 61.8, 61.6,
+
2.5, 42.2, 30.1, 30.0; HRMS (ESI): m/z = 364.11524, calcd. For C H NO Na [M+Na] :
1
9
19
5
64.11554; HPLC (AD-H, 15% iPrOH in Hexanes, 0.75 mL/min, 210 nm): major diastereomer:
tmajor = 16.8 min, tminor = 10.9 min, 92% ee, minor diastereomer: tmajor = 8.6 min, tminor = 13.4 min,
4% ee.
8
Configuration assignment: The absolute configuration of the product (S) was determined by
5
a
comparison of the HPLC retention time with the literature data.
-
1
Compound 6i: white solid (80%); IR (KBr, cm ): ν = 1724, 1685, 1533, 1495, 1447, 1375,
1
1
7
4
7
1
7
261, 1155, 978, 694; H NMR (300 MHz, CDCl ): δ = 8.05 (d, J = 7.5 Hz, 1.3H), 7.86 (d, J =
3
.5 Hz, 0.7H), 7.67-7.37 (m, 3H), 7.33-7.17 (m, 5H), 5.0-4.87 (m, 1.7H), 4.86-4.71 (m, 1.3H),
.55-4.38 (m, 1H), 4.18 (q, J = 14.3, 6.7 Hz, 0.7H), 3.87 (q, J = 14.3, 6.7 Hz, 1.3H), 1.18 (t, J =
1
3
.5, 6.7 Hz, 1H), 0.89 (t, J = 7.5, 6.7 Hz, 2H); C NMR (75.5 MHz, CDCl ): δ = 192.6, 167.5,
3
66.8, 136.5, 136.0, 135.8, 135.6, 134.1, 133.7, 128.8, 128.7, 128.6, 128.4, 128.1, 127.9, 127.8,
7.8, 62.1, 61.8, 56.8, 56.1, 42.9, 13.7, 13.4; HRMS (ESI): m/z = 364.11554, calcd. For
+
C H NO Na [M+Na] : 364.11554; HPLC (OD-H, 10% iPrOH in Hexanes, 1.0 mL/min, 210
19
19
5
nm): major diastereomer: tmajor = 20.4 min, tminor = 36.2 min, 70% ee, minor diastereomer: tmajor
8.3 min, tminor = 16.0 min, 77% ee.
=
1
Configuration assignment: The absolute configuration of the product (S) was determined by
4
b
comparison of the HPLC retention time with the literature data.
-1
Compound 6j: white solid (83%); IR (KBr, cm ): ν = 1717, 1694, 1605, 1557, 1527, 1350,
1
1
8
1
317, 1294, 1254, 1166, 1019, 984, 857, 759, 695; H NMR (300 MHz, CDCl ): δ = 8.33 (d, J =
3
.6 Hz, 1.4H), 8.28-8.17 (m, 2H)), 7.95 (d, J = 8.6 Hz, 0.6H), 7.35-7.15 (m, 5H), 5.03-4.89 (m,
.7H), 4.85-4.79 (m, 1.3H), 4.52-4.38 (m, 1H), 4.21 (q, J = 14.3, 7.1 Hz, 0.6H), 3.89 (q, J = 14.1,

1
3
6
.9 Hz, 1.4H), 1.20 (t, J = 7.1 Hz, 0.9H), 0.91 (t, J = 7.1 Hz, 2.1H); C NMR (75.5 MHz,
CDCl ): δ = 191.7, 166.3, 150.7, 140.1, 136.0, 135.8, 129.8, 129.3, 129.0, 128.5, 128.3, 128.0,
3
1
4
27.9, 123.9, 123.8, 77.8, 62.6, 62.3, 57.4, 56.6, 43.0, 42.8, 13.8, 13.5; HRMS (ESI): m/z =
+
09.10069, calcd. For C H N O Na [M+Na] : 409.10062; HPLC (AD-H, 20% iPrOH in
19
18
2
7
Hexanes, 1.0 mL/min, 210 nm): major diastereomer: tmajor = 8.9 min, tminor = 20.7 min, 87% ee,
minor diastereomer: tmajor = 13.0 min, tminor = 11.6 min, 83% ee.
Configuration assignment: The absolute stereochemistry was assigned as (S) by analogy.
-1
Compound 6k: white solid (85% yield); IR (KBr, cm ): ν 1739, 1704, 1554, 1495, 1453, 1378,
1
1
206, 1140, 704; H NMR (300 MHz, CDCl ): δ = 7.36-7.15 (m, 5H), 5.02 (dd, J = 13.2, 11.1
3
Hz, 0.3H), 4.87 (dd, J = 13.4, 11.5 Hz, 0.7 H), 4.60 (dd, J = 13.2, 3.9 Hz, 0.3H), 4.52 (dd, J =
13.5, 3.9 Hz, 0.7H), 4.38 (dd, J = 11.5, 3.9 Hz, 0.7H), 4.28 (dd, J = 11.1, 3.7 Hz, 0.3H), 2.62-
1
3
2
.50 (m, 1H), 2.32 (s, 2H), 2.18 (s, 1H), 2.13-1.92 (m, 2H), 1.83-1.59 (m, 3H); C NMR (75.5
MHz, CDCl ): δ = 216.8, 213.0, 203.0, 202.7, 135.1, 134.2, 129.3, 129.0, 128.7, 128.6, 128.5,
3
1
28.3, 76.8, 75.4, 71.0, 70.1, 47.0, 46.2, 39.3, 38.5, 30.9, 27.2, 26.5, 19.3, 19.2; HRMS (ESI):
+
m/z = 298.10427, calcd. For C H NO Na [M+Na] : 298.10498; HPLC (AD-H, 20% iPrOH in
15
17
4
Hexanes, 1.0 mL/min, 210 nm): major diastereomer: tmajor = 13.8 min, tminor = 55.9 min, 97% ee,
minor diastereomer: tmajor = 16.8 min, tminor = 26.7 min, 96% ee.
Configuration assignment: The absolute configuration of the product (2S, 3R) was determined
4
b, 5b
by comparison of the HPLC retention time with the literature data.
-1
Compound 6l: white solid (84% yield); IR (KBr, cm ): ν 1746, 1725, 1552, 1453, 1433, 1379,
1
1
233, 1149, 704; H NMR (300 MHz, CDCl ): δ = 7.35-7.20 (m, 5H), 5.16 (dd, J = 3.96, 13.7
3
Hz, 1H), 5.02 (dd, J =10.8, 13.5 Hz, 1H), 4.08 (dd, J = 3.8, 10.8 Hz, 1H), 3.76 (s, 3H), 2.41-2.27
1
3
(
m, 2H), 2.07-1.78 (m, 4H); C NMR (75.5 MHz, CDCl ): δ = 212.1, 169.7, 135.2, 129.2,
3
1
29.1, 129.0, 128.8, 128.4, 128.3, 76.4, 62.4, 53.0, 47.3, 46.1, 39.5, 37.9, 33.4, 31.1, 19.5, 19.3;
+
HRMS (ESI): m/z = 314.09941, calcd. For C H NO Na [M+Na] : 314.09989; HPLC (IC, 10%
15
17
5
iPrOH in Hexanes, 1.0 mL/min, 210 nm): major diastereomer: tmajor = 20.3 min, tminor = 31.7 min,
3% ee.
9
Configuration assignment: The absolute configuration of the product (2S, 3R) was determined
4
b, 5b
by comparison of the HPLC retention time with the literature data.

-1
Compound 6m: pale yellow oil (87% yield); IR (Neat, cm ): ν 1750, 1724, 1554, 1496, 1451,
1
1
1
1
378, 1227, 1150, 769, 704; H NMR (300 MHz, CDCl ): δ = 7.34-7.23 (m, 5H), 5.18 (dd, J =
3
2.8, 3.7 Hz, 1H), 5.02 (dd, J = 13.5, 11.3 Hz, 1H), 4.21 (q, J = 13.5, 6.7 Hz, 2H), 4.08 (dd, J =
13
1.3, 4.5 Hz, 1H), 2.42-2.30 (m, 2H), 2.06-1.79 (m, 4H), 1.27 (t, J = 7.5, 6.7 Hz, 3H); C NMR
(
75.5 MHz, CDCl ): δ = 212.2, 169.2, 135.3, 129.2, 128.7, 128.2, 76.4, 62.3, 62.1, 46.1, 37.8,
3
+
3
1.1, 19.3, 13.9; HRMS (ESI): m/z = 328.11517, calcd. For C H NO Na [M+Na] : 328.11554;
1
6
19
5
HPLC (OD-H, 10% iPrOH in Hexanes, 0.5 mL/min, 210 nm): major diastereomer: tmajor = 25.1
min, tminor = 34.3 min, >99% ee.
Configuration assignment: The absolute configuration of the product (2S, 3R) was determined
5
c
by comparison of the HPLC retention time with the literature data.
-1
Compound 6n: white solid (84% yield); IR (KBr, cm ): ν 1743, 1702, 1557, 1451, 1437, 1382,
1
1
5
3
1
1
204, 1131, 1089, 700; H NMR (300 MHz, CDCl ): δ = 7.31-7.24 (m, 3H), 7.15-7.11 (m, 2H),
3
.06 (dd, J = 3.3, 13.5 Hz, 1H), 4.78 (dd, J = 11.2, 13.5 Hz, 1H), 4.01 (dd, J = 3.3, 11.2 Hz, 1H),
.74 (s, 3H), 2.56-2.50 (m, 1H), 2.47-2.40 (m, 1H), 2.13-2.06(m, 2H), 2.05-1.99 (m, 1H), 1.76-
13
.55 (m, 3H), 1.52-1.44 (m, 1H); C NMR (75.5 MHz, CDCl ): δ = 206.8, 170.0, 135.1, 129.3,
3
28.4, 128.1, 77.3, 62.9, 52.4, 47.5, 41.3, 36.8, 27.8, 22.2; HRMS (ESI): m/z = 328.11498, calcd.
+
For C H NO Na [M+Na] : 328.11554; HPLC (IC, 10% iPrOH in Hexanes, 1.0 mL/min, 210
16
19
5
nm): major diastereomer: tmajor = 16.6 min, tminor = 20.3 min, 96% ee.
Configuration assignment: The absolute configuration of the product (2S, 3R) was determined
5
d
by comparison of the HPLC retention time with the literature data.
-1
Compound 6o: white solid (86% yield); IR (KBr, cm ): ν 1739, 1710, 1554, 1493, 1448, 1425,
1
1
2
376, 1228, 1189, 1086, 704; H NMR (300 MHz, CDCl ): δ = 7.32-7.23 (m, 3H), 7.18-7.11 (m,
3
H), 5.06 (dd, J = 3.2, 13.4 Hz, 1H), 4.80 (dd, J = 11.2, 13.4 Hz, 1H), 4.26-4.16 (m, 2H), 4.00
(dd, J = 3.2, 11.2 Hz, 1H), 2.56-2.41 (m, 2H), 2.13-1.98 (m, 2H), 1.75-1.56 (m, 3H), 1.51-1.43
1
3
(
m, 1H), 1.26 (t, J = 7.1 Hz, 3H); C NMR (75.5 MHz, CDCl ): δ = 207.0, 169.6, 135.3, 129.4,
3
1
28.4, 128.1, 77.5, 62.9, 61.9, 47.7, 41.3, 37.0, 27.9, 22.3, 13.9; HRMS (ESI): m/z = 342.13053,
+
calcd. For C H NO Na [M+Na] : 342.13119; HPLC (IC, 10% iPrOH in Hexanes, 1.0 mL/min,
1
7
21
5
210 nm): major diastereomer: tmajor = 13.4 min, tminor = 16.0 min, 89% ee.

Configuration assignment: The absolute configuration of the product (2S, 3R) was determined
5
e
by comparison of the HPLC retention time with the literature data.
-1
Compound 7b: pale yellow oil (90% yield); IR (Neat, cm ): ν 1750, 1724, 1554, 1515, 1444,
1
1
378, 1227, 1149, 1025, 818; H NMR (300 MHz, CDCl ): δ = 7.15-7.08 (m, 4H), 5.14 (dd, J =
3
3.9, 13.5 Hz, 1H), 4.98 (dd, J = 11.1, 13.4 Hz, 1H), 4.25-4.18 (m, 2H), 4.05 (dd, J = 3.8, 10.9
Hz, 1H), 2.40-2.32 (m, 1H), 2.30 (s, 3H), 2.07-1.86 (m, 4H), 1.86-1.77 (m, 1H), 1.28 (t, J = 7.1
13
Hz, 3H); C NMR (75.5 MHz, CDCl ): δ = 212.3, 169.2, 137.9, 132.1, 129.4, 129.1, 77.1, 62.4,
3
+
6
2.1, 45.8, 37.8, 31.0, 20.9, 19.3, 13.9; ESI-MS: m/z = 342 (M+Na) ; HPLC (IC, 10% iPrOH in
Hexanes, 1.0 mL/min, 210 nm): major diastereomer: tmajor = 16.9 min, tminor = 23.4 min, 92% ee.
Configuration assignment: The absolute stereochemistry was assigned as (2S, 3R) by analogy.
-1
Compound 7c: pale yellow oil (94% yield); IR (Neat, cm ): ν 1750, 1723, 1611, 1553, 1514,
1
1
2
4
443, 1379, 1253, 1228, 1182, 1032, 837; H NMR (300 MHz, CDCl ): δ = 7.18 (d, J = 8.7 Hz,
3
H), 6.82 (d, J = 8.7 Hz, 2H), 5.11 (dd, J = 3.8, 13.2 Hz, 1H), 4.96 (dd, J = 11.1, 13.2 Hz, 1H),
.25-4.16 (m, 2H), 4.05 (dd, J = 3.8, 11.1 Hz, 1H), 3.77 (s, 3H), 2.41-2.30 (m, 2H), 2.05-1.87
1
3
(
m, 3H), 1.86-1.77 (m, 1H), 1.27 (t, J = 7.1 Hz, 3H); C NMR (75.5 MHz, CDCl ): δ = 212.3,
3
1
69.3, 159.2, 130.3, 126.9, 114.0, 76.5, 62.5, 62.0, 55.1, 45.4, 37.8, 30.9, 19.3, 13.8; ESI-MS:
+
m/z = 358 (M+Na) ; HPLC (IC, 10% iPrOH in Hexanes, 1.0 mL/min, 210 nm): major
diastereomer: tmajor = 23.1 min, tminor = 29.6 min, 98% ee.
Configuration assignment: The absolute stereochemistry was assigned as (2S, 3R) by analogy.
-1
Compound 7f: pale yellow oil (92% yield); IR (Neat, cm ): ν 1750, 1724, 1554, 1511, 1443,
1
1
378, 1228, 1162, 1020, 844; H NMR (300 MHz, CDCl ): δ = 7.29-7.25 (m, 2H), 7.03-6.97 (m,
3
2H), 5.15 (dd, J = 3.8, 13.5 Hz, 1H), 4.97 (dd, J = 11.1, 13.4 Hz, 1H), 4.24-4.17 (m, 2H), 4.05
(dd, J = 3.6, 11.1 Hz, 1H), 2.42-2.33 (m, 2H), 2.09-2.01 (m, 1H), 1.98-1.90 (m, 2H), 1.89-1.80
1
3
(
m, 1H), 1.27 (t, J = 7.1 Hz, 3H); C NMR (75.5 MHz, CDCl ): δ = 212.2, 169.2, 164.0, 160.7,
3
1
31.1, 130.9, 115.8, 115.5, 76.4, 62.3, 62.2, 45.4, 37.7, 31.2, 19.2, 13.8; ESI-MS: m/z = 346
+
(
M+Na) ; HPLC (IC, 10% iPrOH in Hexanes, 1.0 mL/min, 210 nm): major diastereomer: t
=
major
1
4.8 min, tminor = 19.5 min, 95% ee.

Configuration assignment: The absolute configuration of the product (2S, 3R) was determined
4
e
by comparison of the HPLC retention time with the literature data.
-1
Compound 7g: pale yellow oil (94% yield); IR (Neat, cm ): ν 1728, 1555, 1514, 1493, 1445,
1
1
7
2
1
1
378, 1231, 1175, 1094, 1016, 855; H NMR (300 MHz, CDCl ): δ = 7.31-7.26 (m, 2H), 7.25-
3
.20 (m, 2H), 5.15 (dd, J = 3.6, 13.7 Hz, 1H), 4.97 (dd, J = 11.1, 13.5 Hz, 1H), 4.28-4.17 (m,
H), 4.03 (dd, J = 3.6, 11.1 Hz, 1H), 2.49-2.33 (m, 2H), 2.13-2.02 (m, 1H), 1.99-1.81 (m, 3H),
13
.27 (t, J = 7.1 Hz, 3H); C NMR (75.5 MHz, CDCl ): δ = 212.0, 169.1, 134.2, 133.9, 130.7,
3
+
28.9, 76.2, 62.2, 45.5, 37.7, 31.4, 19.2, 13.9; ESI-MS: m/z = 362 (M+Na) ; HPLC (IC, 10%
iPrOH in Hexanes, 1.0 mL/min, 210 nm): major diastereomer: tmajor = 14.4 min, tminor = 18.0 min,
8% ee.
9
Configuration assignment: The absolute stereochemistry was assigned as (2S, 3R) by analogy.
-1
Compound 7h: pale yellow oil (91% yield); IR (Neat, cm ): ν 1752, 1725, 1554, 1489, 1443,
1
1
377, 1229, 1159, 1011, 820; H NMR (300 MHz, CDCl ): δ = 7.50-7.40 (m, 2H), 7.22-7.13 (m,
3
2H), 5.16 (dd, J = 3.7, 13.5 Hz, 1H), 4.97 (dd, J = 10.5, 13.5 Hz, 1H), 4.29-4.16 (m, 2H), 4.02
(dd, J = 3.7, 11.3 Hz, 1H), 2.56-2.27 (m, 3H), 2.18-2.06 (m, 1H), 2.03-1.80 (m, 2H), 1.27 (t, J =
1
3
7
.5, 6.7 Hz, 3H); C NMR (75.5 MHz, CDCl ): δ = 212.1, 169.1, 134.4, 131.9, 131.0, 122.4,
3
7
6.1, 62.5, 62.3, 62.1, 45.6, 37.7, 35.8, 34.7, 31.4, 19.3, 18.3, 14.0, 13.9; ESI-MS: m/z = 406
+
(
M+Na) ; HPLC (IC, 10% iPrOH in Hexanes, 1.0 mL/min, 210 nm): major diastereomer: t
=
major
1
6.2 min, tminor = 20.9 min, 97% ee.
Configuration assignment: The absolute stereochemistry was assigned as (2S, 3R) by analogy.
-1
Compound 7k: yellow oil (93% yield); IR (Neat, cm ): ν 1750, 1726, 1555, 1492, 1453, 1378,
1
1
228, 1149, 1021, 762; H NMR (300 MHz, CDCl ): δ = 7.45-7.39 (m, 1H), 7.31-7.25 (m, 1H),
3
7.15-7.09 (m, 1H), 7.08-7.02 (m, 1H), 5.37 (dd, J = 3.6, 14.0 Hz, 1H), 5.13 (dd, J = 10.6, 14.0
Hz, 1H), 4.28 (dd, J = 3.5, 10.5 Hz, 1H), 4.24-4.17 (m, 2H), 2.49-2.40 (m, 1H), 2.37-2.27 (m,
1
3
2
1
3
2
H), 2.02-1.85 (m, 3H), 1.27 (t, J = 7.3, 7.1 Hz, 3H); C NMR (75.5 MHz, CDCl ): δ = 212.3,
3
68.9, 162.7, 130.4, 130.0, 129.8, 124.7, 124.6, 115.9, 115.6, 75.7, 62.1, 61.3, 39.2, 38.0, 37.7,
+
2.3, 19.0, 13.9; ESI-MS: m/z = 346 (M+Na) ; HPLC (IC, 10% iPrOH in Hexanes, 1.0 mL/min,
10 nm): major diastereomer: tmajor = 15.2 min, tminor = 17.9 min, 97% ee.

Configuration assignment: The absolute stereochemistry was assigned as (2S, 3R) by analogy.
-1
Compound 7l: yellow oil (89% yield); IR (Neat, cm ): ν 1750, 1726, 1554, 1475, 1440, 1378,
1
1
7
3
228, 1160, 1037, 759; H NMR (300 MHz, CDCl ): δ = 7.59-7.53 (m, 1H), 7.41-7.36 (m, 1H),
3
.30-7.18 (m, 2H), 5.48 (dd, J = 3.5, 13.9 Hz, 1H), 5.09 (dd, J = 10.5, 13.7 Hz, 1H), 4.53 (dd, J =
.5, 10.7 Hz, 1H), 4.21 (q, J = 6.9, 7.1 Hz, 2H), 2.53-2.44 (m, 2H), 2.32-2.20 (m, 1H), 2.15-2.02
1
3
(
m, 1H), 2.00-1.87 (m, 2H), 1.26 (t, J = 7.1, 6.9 Hz, 3H); C NMR (75.5 MHz, CDCl ): δ =
3
2
12.8, 169.4, 135.6, 134.8, 130.2, 129.4, 129.1, 127.7, 77.1, 62.2, 41.0, 37.9, 33.0, 19.4, 14.0;
+
ESI-MS: m/z = 362 (M+Na) ; HPLC (IC, 10% iPrOH in Hexanes, 1.0 mL/min, 210 nm): major
diastereomer: tmajor = 17.0 min, tminor = 20.3 min, 97% ee.
Configuration assignment: The absolute configuration of the product was determined by
4
e
comparison of the HPLC retention time with the literature data.
-1
Compound 7m: yellow oil (90% yield); IR (Neat, cm ): ν 1750, 1726, 1554, 1470, 1438, 1377,
1
1
7
3
1
1
227, 1160, 1024, 759; H NMR (300 MHz, CDCl ): δ = 7.60-7.54 (m, 2H), 7.33-7.28 (m, 1H),
3
.16-7.12 (m, 1H), 5.47 (dd, J = 3.5, 13.8 Hz, 1H), 5.06 (dd, J = 10.6, 13.7 Hz, 1H), 4.51 (dd, J =
.5, 10.5 Hz, 1H), 4.20 (q, J = 7.1 Hz, 2H), 2.52-2.44 (m, 2H), 2.25-2.18 (m, 1H), 2.14-2.07 (m,
1
3
H), 2.00-1.89 (m, 2H), 1.26 (t, J = 7.1 Hz, 3H); C NMR (75.5 MHz, CDCl ): δ = 212.5, 169.3,
3
36.5, 133.4, 129.5, 129.0, 128.2, 126.7, 62.3, 62.14, 62.10, 43.8, 37.7, 33.0, 19.3, 13.9; ESI-
+
MS: m/z = 406 (M+Na) ; HPLC (IC, 10% iPrOH in Hexanes, 1.0 mL/min, 210 nm): major
diastereomer: tmajor = 18.2 min, tminor = 21.6 min, 98% ee.
Configuration assignment: The absolute stereochemistry was assigned as (2S, 3R) by analogy.
-1
Compound 7n: yellow oil (92% yield); IR (Neat, cm ): ν 1751, 1725, 1556, 1529, 1446, 1353,
1
1
229, 1172, 1017, 856, 752; H NMR (300 MHz, CDCl ): δ = 8.08 (d, J = 8.2 Hz, 0.2H), 7.97 (d,
3
J = 7.8 Hz, 0.2H), 7.88 (d, J = 8.0 Hz, 0.7H), 7.81 (d, J = 8.2 Hz, 0.7H), 7.78-7.73 (m, 0.3H),
7
5
0
2
3
1
.62-7.59 (m, 0.9H), 7.58-7.53 (m, 0.3H), 7.47-7.43 (m, 0.8H), 5.37 (dd, J = 3.5, 14.3 Hz, 0.9H),
.06 (dd, J = 10.6, 14.3 Hz, 0.8H), 4.88 (dd, J = 1.6, 13.2 Hz, 0.2H), 4.66 (dd, J = 3.5, 10.6 Hz,
.8H), 4.56 (dd, J = 9.1, 13.7 Hz, 0.2H), 4.21 (q, J = 7.1 Hz, 1.8H), 4.12 (q, J = 7.1 Hz, 0.2H),
.57-2.42 (m, 2H), 2.24-2.16 (m, 1H), 2.09-2.00 (m, 2H), 1.98-1.86 (m, 1H), 1.26 (t, J = 7.1 Hz,
1
3
H); C NMR (75.5 MHz, CDCl ): δ = 212.7, 169.9, 134.3, 133.1, 131.6, 129.6, 129.5, 128.9,
3
28.6, 124.9, 124.8, 76.9, 66.7, 62.3, 61.5, 38.9, 37.5, 33.5, 19.2, 13.8; ESI-MS: m/z = 373

+
(
M+Na) ; HPLC (IC, 15% iPrOH in Hexanes, 1.0 mL/min, 210 nm): major diastereomer: t
=
major
4
1.5 min, tminor = 31.5 min, 99% ee.
Configuration assignment: The absolute stereochemistry was assigned as (2S, 3R) by analogy.
-1
Compound 7s: yellow oil (94% yield); IR (Neat, cm ): ν 1750, 1725, 1555, 1532, 1445, 1378,
1
1
1
1
350, 1230, 1158, 1018, 693; H NMR (300 MHz, CDCl ): δ = 8.28-8.21 (m, 1H), 8.19-8.13 (m,
3
H), 7.73-7.67 (m, 1H), 7.56-7.50 (m, 1H), 5.29 (dd, J = 3.5, 14.1 Hz, 1H), 5.08 (dd, J = 11.1,
4.0 Hz, 1H), 4.29-4.18 (m, 2H), 4.10 (dd, J = 3.5, 10.9 Hz, 1H), 2.51-2.42 (m, 1H), 2.38-2.30
13
(
m, 1H), 2.22-2.11 (m, 1H), 2.04-1.87 (m, 3H), 1.28 (t, J = 7.1 Hz, 3H); C NMR (75.5 MHz,
CDCl ): δ = 211.9, 169.0, 148.2, 137.9, 135.9, 129.7, 124.0, 123.2, 75.9, 62.5, 61.8, 45.8, 37.6,
3
+
3
2.1, 19.2, 13.8; ESI-MS: m/z = 373 (M+Na) ; HPLC (IC, 15% iPrOH in Hexanes, 1.0 mL/min,
10 nm): major diastereomer: tmajor = 22.2 min, tminor = 30.5 min, 95% ee.
2
Configuration assignment: The absolute stereochemistry was assigned as (2S, 3R) by analogy.
-1
Compound 7t: yellow oil (91% yield); IR (Neat, cm ): ν 1749, 1724, 1553, 1513, 1442, 1378,
1
1
226, 1152, 1021, 778, 757; H NMR (300 MHz, CDCl ): δ = 8.21 (d, J = 8.6 Hz, 1H), 7.85-7.77
3
(m, 2H), 7.64-7.55 (m, 2H), 7.52-7.42 (m, 2H), 5.51 (dd, J = 3.8, 13.7 Hz, 1H), 5.15 (dd, J =
1
2
2
3
0.3, 13.5 Hz, 1H), 5.00 (dd, J = 3.8, 10.3 Hz, 1H), 4.26-4.18 (m, 2H), 2.45-2.37 (m, 1H), 2.30-
1
3
.18 (m, 2H), 1.92-1.82 (m, 3H), 1.25 (t, J = 7.1 Hz, 3H); C NMR (75.5 MHz, CDCl ): δ =
3
12.3, 169.3, 133.9, 133.0, 132.5, 128.9, 126.7, 125.8, 125.4, 125.1, 122.9, 77.7, 62.8, 62.1, 38.9,
+
7.7, 32.4, 19.3, 13.9; ESI-MS: m/z = 378 (M+Na) ; HPLC (IC, 10% iPrOH in Hexanes, 1.0
mL/min, 210 nm): major diastereomer: tmajor = 17.0 min, tminor = 21.8 min, 93% ee.
Configuration assignment: The absolute configuration of the product was determined by
4
e
comparison of the HPLC retention time with the literature data.
-1
Compound 7o: yellow oil (95% yield); IR (Neat, cm ): ν 1749, 1723, 1553, 1509, 1441, 1377,
1
1
1
1
228, 1150, 1020, 821, 753; H NMR (300 MHz, CDCl ): δ = 7.82-7.77 (m, 3H), 7.73-7.71 (m,
3
H), 7.50-7.46 (m, 2H), 7.41-7.38 (m, 1H), 5.25 (dd, J = 3.8, 13.7 Hz, 1H), 5.15 (dd, J = 10.8,
3.5 Hz, 1H), 4.27-4.20 (m, 3H), 2.42-2.32 (m, 2H), 2.08-1.99 (m, 2H), 1.97-1.78 (m, 2H), 1.28
1
3
(
t, J = 7.1 Hz, 3H); C NMR (75.5 MHz, CDCl ): δ = 212.3, 169.3, 133.0, 132.9, 132.8, 128.8,
3
1
28.6, 127.9, 127.5, 126.6, 126.5, 126.4, 76.5, 62.5, 62.2, 46.3, 37.8, 31.4, 19.3, 13.9; ESI-MS:

+
m/z = 378 (M+Na) ; HPLC (IC, 10% iPrOH in Hexanes, 1.0 mL/min, 210 nm): major
diastereomer: tmajor = 20.3 min, tminor = 26.1 min, 97% ee.
Configuration assignment: The absolute configuration of the product (2S, 3R) was determined
5
g
by comparison of the HPLC retention time with the literature data.
-1
Compound 7p: pale yellow oil (93% yield); IR (Neat, cm ): ν 1752, 1724, 1557, 1503, 1447,
1
1
379, 1230, 1146, 1017, 916, 744; H NMR (300 MHz, CDCl ): δ = 7.34 (d, J = 1.2 Hz, 1H),
3
6.30 (dd, J = 1.8, 3.2 Hz, 1H), 6.19 (d, J = 3.2 Hz, 1H), 4.97-4.88 (m, 2H), 4.44 (dd, J = 4.4, 10.0
Hz, 1H), 4.25-4.18 (m, 2H), 2.51-2.45 (m, 1H), 2.39-2.31 (m, 1H), 2.16-2.09 (m, 1H), 2.03-1.94
1
3
(
m, 2H), 1.78-1.70 (m, 1H), 1.28 (t, J = 7.1 Hz, 3H); C NMR (75.5 MHz, CDCl ): δ = 212.0,
3
1
3
68.8, 149.0, 142.6, 110.7, 110.0, 74.4, 62.2, 61.8, 40.3, 37.8, 30.1, 19.4, 13.9; ESI-MS: m/z =
+
18 (M+Na) ; HPLC (IC, 10% iPrOH in Hexanes, 1.0 mL/min, 210 nm): major diastereomer:
tmajor = 9.8 min, tminor = 14.2 min, 95% ee.
Configuration assignment: The absolute configuration of the product (2S, 3R) was determined
4
e
by comparison of the HPLC retention time with the literature data.
-1
Compound 7q: yellow oil (92% yield); IR (Neat, cm ): ν 1748, 1723, 1555, 1439, 1378, 1228,
1
1
6
3
1
1
147, 1023, 853, 708; H NMR (300 MHz, CDCl ): δ = 7.25-7.21 (m, 1H), 6.97-6.95 (m, 1H),
3
.94-6.91 (m, 1H), 5.13 (dd, J = 3.5, 13.5 Hz, 1H), 4.93 (dd, J = 10.6, 13.5 Hz, 1H), 4.42 (dd, J =
.5, 10.5 Hz, 1H), 4.23 (q, J = 7.1 Hz, 2H), 2.47-2.37 (m, 2H), 2.18-2.06 (m, 2H), 2.05-1.97 (m,
1
3
H), 1.94-1.85 (m, 1H), 1.29 (t, J = 7.1 Hz, 3H); C NMR (75.5 MHz, CDCl ): δ = 212.3, 169.2,
3
+
37.4, 128.6, 126.7, 126.0, 77.5, 62.2, 42.0, 37.9, 31.5, 19.3, 13.9; ESI-MS: m/z = 334 (M+Na) ;
HPLC (IC, 10% iPrOH in Hexanes, 1.0 mL/min, 225 nm): major diastereomer: tmajor = 12.3 min,
tminor = 19.9 min, 75% ee.
Configuration assignment: The absolute configuration of the product (2S, 3R) was determined
5
f
by comparison of the HPLC retention time with the literature data.
-1
Compound 7r: pale yellow oil (94% yield); IR (Neat, cm ): ν 1750, 1724, 1554, 1490, 1446,
1
1
2
2
378, 1249, 1160, 1038, 934, 815; H NMR (300 MHz, CDCl ): δ = 6.80 (s, 1H), 6.74-6.67 (m,
3
H), 5.94 (s, 2H), 5.13 (dd, J = 3.7, 13.5 Hz, 1H), 4.95 (dd, J = 11.3, 13.5 Hz, 1H), 4.28-4.16 (m,
H), 3.95 (dd, J = 3.7, 10.5 Hz, 1H), 2.51-2.32 (m, 3H), 2.17-2.04 (m, 1H), 2.01-1.80 (m, 2H),

1
3
1
.27 (t, J = 7.5, 6.7 Hz, 3H); C NMR (75.5 MHz, CDCl ): δ = 212.3, 169.3, 147.8, 147.4,
3
1
28.8, 123.0, 109.3, 108.2, 101.1, 76.6, 62.4, 62.1, 45.9, 37.7, 35.7, 34.6, 31.3, 19.2, 18.2, 13.8;
+
ESI-MS: m/z = 372 (M+Na) ; HPLC (IC, 10% iPrOH in Hexanes, 1.0 mL/min, 210 nm): major
diastereomer: tmajor = 29.8 min, tminor = 34.9 min, 99% ee.
Configuration assignment: The absolute stereochemistry was assigned as (2S, 3R) by analogy.

1
13
4
) H and C NMR spectra of catalysts 1k, 1l, 1a-j and products 4, 6 and 7