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Chiral Olefin–Sulfoxide as Ligands for Rhodium-Catalyzed Asymmetric Conjugate Addition of Arylboronic Acids to Unsaturated Esters Published on 27 September 2013. Downloaded by Drexel University on 28/09/2013 08:28:20.

Feng Xuea,b, Dongping Wanga, Xincheng Lia, Boshun Wan*,a Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX DOI: 10.1039/b000000x

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An efficient rhodium/olefin–sulfoxide catalyzed asymmetric conjugate addition of organoboronic acids to various unsaturated esters has been developed, where 2-methoxy-1naphthyl sulfinyl functionalized olefin ligands have shown to be highly effective, and are especially applicable to unsaturated methyl esters with up to 99% yield and 91% ee.

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Introduction Pioneered by Miyaura and Hayashi, the Rh-catalyzed enantioselective conjugate addition of organoboron reagents to electron deficient olefins has developed into a powerful tool for the stereoselective formation of carbon-carbon bonds and has become been increasingly explored.1 Many exciting results have been achieved in the asymmetric addition to α,βunsaturated carbonyl compounds2 and related aldimines3 with olefin-based ligands. Our assumption of olefin-sulfoxide skeleton as a new class of effective ligands for asymmetric catalysis comes from elegant performances of both olefinoxazoline4 and bis-sulfoxide5 ligands based on benzene backbone in 1,4-addition reactions. We assume that using ophenylene as the linkage of olefin and sulfoxide is beneficial not only because of its rigid skeleton, which is crucial for the asymmetric induction, but also its easy accessibility. Furthermore, the diversity of olefin and sulfinyl functionalities allows this kind of ligand to be easily modified, which is highly important for the ligand design. Thus, the highly modular and easily tunable olefin–sulfoxide ligands bearing different olefin and sulfinyl moieties were prepared to form a series of electronically and sterically varied benzene backbone-based olefin–sulfoxide ligands in facile two-step synthesis (Scheme 1).6,7 The olefin–sulfoxide ligands (1) can be well applied for the Rh-catalyzed enantioselective addition of arylboronic acids to enones with excellent enantioselectivities ( up to 97% ee). 6 Subsequently, an efficient rhodium/olefin–sulfoxide catalyzed asymmetric conjugate addition of organoboronic acids to a variety of nitroalkenes has also been developed, where 2-methoxy-1-naphthyl sulfinyl functionalized olefin

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This journal is © The Royal Society of Chemistry [The year]

Br

sulfoxide O S R1 benzene backbone Olefin

R

R1 CH2Br

Ar

Ar

O S R11=-OMe R1 R12= -OMOM 1

O C H

O S R'

R

a: R1 = t- Bu R b: R2 = p- Tol c: R3 = p- MeOC6H4 d: R4 = 2-MeO-1-naphthyl

Ar a: Ar1 = Ph 2 b: Ar = 4-MeOC6H4 c: Ar3 = 2,4,6-(MeO)3C6H2 d: Ar4 =4-FC6H4

Wan's olefin-sulfoxide ligands 50

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Scheme 1. Modular olefin–sulfoxide ligand by assembly, retrosynthetic procedure. Despite great progress made in the the Rh-catalyzed enantioselective addition reactions,10,11 related studies focusing on the scope of reactions and the type of olefin– sulfoxide ligands remained elusive and limited. It is still highly desirable to develop effective catalytic systems for the asymmetric addition to a broad scope of acceptors using the highly modular and easily tunable olefin–sulfoxide ligands. Me

O O Me

S

Ph

Ph Me

a

Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, P. R. China. E-mail: [email protected] b College of Chemistry and Chemical Engineering, Henan Institute of Science and Technology, Xinxiang Henan, 453002, P. R. China. † Electronic Supplementary Information (ESI) available: Experimental details. See DOI: 10.1039/b000000x/

ligands have shown to be highly effective, and are applicable to a broad scope of aryl, alky and heteroaryl nitroalkenes with high enantioselectivities ( up to 91% ee).7 In the meantime, other sulfinyl–based olefin ligands have also been successfully developed and applied in the Rh-catalyzed enantioselective addition reactions.8,9

Me

2

Ph

3

Me

Previous work 60

R

R1

Ar

1 This work

Figure 1. Ligands Used in the Asymmetric Addition Reaction of Arylboronic Acids to Linear Unsaturated Esters. [journal], [year], [vol], 00–00 | 1

Organic & Biomolecular Chemistry Accepted Manuscript

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Up to now, despitie great progress made in the reaction of cyclic enones and unsaturated esters, related studies focusing on linear unsaturated esters remained fewer (Figure 1). 12-15 We wondered whether these rhodium/ olefin-sulfoxide complexes could also act as effective catalysts for the asymmetric addition of boronic acids to various unsaturated esters. Herein we describe our efforts to address this issue. By employing olefin-sulfoxide as a ligand, aryl boronic acids were effectively activated under rhodium catalysis to react stereoselectively with linear unsaturated esters, giving products with moderate to high yields and good enantioselectivities under mild conditions.

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Results and discussion

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Initially, we examined the Rh-catalyzed reaction of methyl cinnamate with 4-methoxybenzeneboronic acid in the presence of olefin-sulfoxide ligand 1a (Scheme 2 ) using the conditions previously reported for the addition of arylboronic acids to nitroalkenes.7 To our disappointment, the product 6a was obtained in only 46% yield, albeit with moderate enantioselectivity (43% ee, Table 1,entry 1).

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1e 1f 1g 1h 1i 1j 1k 1l 1m

69 72 75 72 78 70 72 73 80

63 61 74 70 82 78 55 61 85

a The reaction was carried out with methyl cinnamate (0.30 mmol), para-anisylboronic acid (0.90 mmol), [RhCl(C2H4)2]2 (0.0075 mmol), ligand (0.0165 mmol, 1.1 equiv to Rh), and 0.75 M aq KOH (0.20 mL) in toluene (2.0 mL) at 100 °C for 12 h. b Isolated yield based on methyl cinnamate. c Determined by HPLC analysis.

After ligand 1m was established as the optimal ligand, other reaction conditions were further investigated, as shown in Table 2. The solvents showed little influence on the ee value, but had a drastic effect on the product yield (entries 1–4). Careful screening indicated that THF was the best solvent for both good yield and enantioselectivity (entry 3). A further survey of inorganic bases such as K3PO4, K2HPO4, KF and organic base such as Et3N did not improve the yield and enantioselectivity of the reaction (entries 5–9). Combination of potassium acid fluoride with organoboron reagents to in situ generate reactive organotrifluoroborates did not yet increase the reactivity and enantioselectivity (entry 10). Table 2. Optimization of the Reaction Conditions.a

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Scheme 2. Olefin–Sulfoxide Ligands 1 with Diverse Structures.

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Among the ligands (Scheme 2, 1b–1d) with different sulfinyl moieties subsequently screened, ligand bearing a 2methoxy-1-naphthyl sulfinyl moiety afforded the promising result with 70% yield and 67% ee (Table 1, entry 4). After careful screening on the substitution effects on the central benzene ring moiety and terminal benzene ring moiety, we found that ligand 1m afforded the satisfying result with 80% yield and 85% (Table 1, entry 13). Table 1. Screening of Ligands in the Conjugate Addition Reaction.

ligand

1 2 3 4

1a 1b 1c 1d

yieldb (%) 46 81 77 70

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eec (%) 43 35 30 67

solvent

additive

yieldb (%)

1d 2 3 4 5 6 7 8 9e 10f

CH2Cl2 dioxane THF MeOH THF THF THF THF THF THF

KOH KOH KOH KOH K3PO4 K2HPO4 K2CO3 KF Et3N KHF2

65 50 85 54 76 80 72 75 67 79

eec (%) 89 88 89 87 90 89 89 89 87 89

a

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entry

entry

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The reaction was carried out with methyl cinnamate (0.30 mmol), para-anisylboronic acid (0.90 mmol), [RhCl(C 2 H4 )2]2 (0.0075 mmol), ligand 1m (0.0165 mmol, 1.1 equiv to Rh), and additive (0.75 M aq, 0.20 mL, 0.5 equiv) in the indicated solvent (2 mL) for 12 h. b Isolated yield based on methyl cinnamate. c Determined by HPLC analysis. d The reaction proceeded at 40 °C. e The reaction proceeded at 60 °C. f Et 3N (22 µL, 0.5 equiv), g KHF2 (4.5 M aq, 0.20 mL, 3 equiv).

With the optimal reaction conditions in hand, the scope of this reaction was screened. A variety of representative boronic acids and unsaturated esters were subjected to this reaction under the optimal conditions, and the results were summarized in Table 3. Compared with tert-butyl-, ethyl- and benzyl cinnamates, methyl cinnamate gave better result with 85% yield and 89% ee (entries 1–4). It is worth mentioning that when it comes to ethyl cinnamate, higher enantioselecitivity was obtained than that in previously work (entry 3, 89% ee versus 65% ee14). The electronic properties of boronic acids did not affect the stereoselectivity significantly. In contrast, sterically more hindered arylboronic acids had a significant impact on the

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Organic & Biomolecular Chemistry Accepted Manuscript

DOI: 10.1039/C3OB41342J

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Addition of Arylboronic Acids to Unsaturated Esters.

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entry

Ar

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17

Ph Ph Ph Ph Ph Ph Ph Ph Ph Ph Ph Ph Ph Ph 4-MeOC6H4 4-FC6H4 4-FC6H43

R

Ar

Me tBu Et Bn Me Me Me Me Me Me Me Me Me Me Me Me Me

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4-MeOC6H4 4-MeOC6H4 4-MeOC6H4 4-MeOC6H4 2-MeOC6H4 4-MeC6H4 4- tBuC6H4 1-naph 2-naph 3,4-DiMeOC6H4 Ph Ph Ph 4-MeOC6H4 4-MeOC6H4 4-MeOC6H4 4-MeOC6H4

yieldb (%) 85 (6a) 62 (6b) 81 (6c) 83(6d) 76 (6e) 92 (6f) 91 (6g) 60 (6h) 99 (6i) 95 (6j) 93 (6k) 88 (6l) 73 (6m) 92 (6n) 83 (6o) 85 (6p) 62 (6q)

eec (%) 89 87 89 70 89 86 89 83 79 88 89 89 91 91 90 90 90

a

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The reaction was carried out with unsaturated esters (0.30 mmol), arylboronic acids (0.90 mmol), [RhCl(C2H4)2]2 (0.0075 mmol), ligand 1m (0.0165 mmol, 1.1 equiv to Rh), and 0.75 M aq KOH (0.20 mL) in THF (2.0 mL) at 60 °C for 12 h. b Isolated yield based on unsaturated esters. c Determined by HPLC analysis.

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Conclusion

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In summary, we have developed an efficient rhodium/olefin– sulfoxide catalyzed asymmetric conjugate addition of organoboronic acids to linear unsaturated esters, which gave moderate to high yields and good enantioselectivities by using 2-methoxy-1-naphthyl sulfinyl-based olefin ligand. A range of tert-butyl-, ethyl-, benzyl-, methyl cinnamates can be well tolerated in this process. Further development of more effective chiral olefin–sulfoxide hybrid ligands and their applications in other asymmetric reactions are currently underway in our laboratory.

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Experimental section

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General Considerations All reactions were carried out under an atmosphere of nitrogen using standard Schlenk techniques, unless otherwise noted. Commercially available reagents were used throughout without further purification other than those detailed below. THF, Et2O and toluene were distilled over sodium/benzopheneone under nitrogen. Methylene chloride was distilled over calcium hydride. Arylboronic acids were recrystallized from water. The synthesis of ligand 1a–1m has been reported. Please see reference 6,7 for details. General

Procedure

for

the

Asymmetric

Conjugate

This journal is © The Royal Society of Chemistry [The year]

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Under nitrogen atmosphere, a mixture of [RhCl(C2H4)2]2 (2.9 mg, 0.0075 mmol) and ligand 1m (7.4 mg, 0.0165 mmol) in 1 mL THF was stirred at room temperature for 1 h. At which time arylboronic acid (0.90 mmol) was added, followed by unsaturated esters (0.30 mmol), aqueous KOH (0.75 M in H2O, 0.20 mL, 0.15 mmol) and THF (1 mL). The reaction was stirred at 60 °C for 12 h. When the reaction was over, the reaction mixture was concentrated in vacuo and purified by silica gel flash column chromatography (petroleum ether/ethyl acetate as eluent) to afford the product. Methyl 3-(4-methoxyphenyl)-3-phenylpropanoate (6a). 16 White solid, mp 43–45 °C, 69 mg, 85% yield, 89% ee; [α]23D = –2.3 (c = 1.2, CHCl3); HPLC: Chiracel OD-H column, detected at 230 nm, n-hexane/i-propanol = 90/10, flow = 1.0 mL/min (44 bar), tR = 7.3 min (minor) and 9.8 min (major); 1H NMR (400 MHz, CDCl3): δ 7.34–7.07 (m, 7H), 6.81 (d, J = 7.6 Hz, 2H), 4.51 (t, J = 7.8 Hz, 1H), 3.75 (s, 3H), 3.57 (s, 3H), 3.03 (d, J = 7.9 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 172.4, 158.3, 143.9, 135.7, 128.7 (d, J = 5.4 Hz), 127.6, 126.6, 114.0, 77.5, 77.2, 76.8, 55.3, 51.8, 46.3, 40.9; HRMS (ESI, m/z) calcd for C17H18O3Na [M + Na] + 293.1154, found 293.1156. Butyl 3-(4-methoxyphenyl)-3-phenylpropanoate (6b). 14 White solid, mp 59–61 °C , 59 mg, 62% yield, 87% ee; [α]23D = 0.7 (c = 0.8, CHCl3); HPLC: Chiracel AD-H column, detected at 230 nm, n-hexane/i-propanol = 98/2, flow = 1.0 mL/min (37 bar), tR = 9.3 min (major) and 10.5 min (minor); 1 H NMR (400 MHz, CDCl3): δ 7.20 (dd, J = 36.4, 7.0 Hz, 7H), 6.92–6.73 (m, 2H), 4.50–4.31 (m, 1H), 3.76 (s, 3H), 3.00– 2.85 (m, 2H), 1.27 (s, 9H); 13C NMR (100 MHz, CDCl3): δ 171.3, 144.1, 135.9, 128.8, 128.6, 127.8, 126.5, 113.9, 80.6, 55.4, 46.8, 42.4, 28.0; HRMS (ESI, m/z) calcd for C20H24O3Na [M + Na]+ 335.1623, found 335.1626. Ethyl 3-(4-methoxyphenyl)-3-phenylpropanoate (6c).14 Colorless oil, 69 mg, 81% yield, 89% ee; [α] 23D = –1.5 (c = 1.5, CHCl3); HPLC: Chiracel AD-H column, detected at 230 nm, n-hexane/i-propanol = 98/2, flow = 1.0 mL/min (36 bar), tR = 14.7 min (major) and 15.6 min (minor); 1H NMR (400 MHz, CDCl3): δ 7.31–7.11 (m, 7H), 6.81 (d, J = 8.6 Hz, 2H), 4.50 (t, J = 8.0 Hz, 1H), 4.02 (q, J = 7.1 Hz, 2H), 3.74 (s, 3H), 3.01 (d, J = 8.1 Hz, 2H), 1.10 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 171.9, 158.2, 143.9, 135.7, 128.7, 128.6, 127.7, 126.5, 113.9, 60.5, 55.24, 46.4, 41.1, 14.2; HRMS (ESI, m/z) calcd for C18H20O3Na [M + Na] + 307.1310, found 307.1317. Benzyl 3-(4-methoxyphenyl)-3-phenylpropanoate (6d). 14 White solid, mp 69–70 °C, 86 mg, 83% yield, 70% ee; [α]23D = –2.1 (c = 1.2, CHCl3); HPLC: Chiracel AD-H column, detected at 230 nm, n-hexane/i-propanol = 98/2, flow = 1.0 mL/min (36 bar), tR = 28.7 min (major) and 34.2 min (minor); 1 H NMR (400 MHz, CDCl 3): δ 7.41–7.04 (m, 12H), 6.80 (d, J = 8.5 Hz, 2H), 5.01 (s, 2H), 4.52 (t, J = 8.1 Hz, 1H), 3.75 (s, 3H), 3.08 (d, J = 8.1 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 171.9, 158.3, 143.8, 135.9, 135.6, 128.8, 128.7, 128.6, 128.2, 127.7, 126.6, 114.1, 66.4, 55.3, 46.4, 41.2; HRMS (ESI, m/z) [journal], [year], [vol], 00–00 | 3

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reactivity, as demonstrated in the reaction of 1-naphthylboronic acid and 2-methoxylboronic acid (entries 5 and 8). For electrondeficient unsaturated esters, the electron-deficient boronic acids had no effect on the enantioselectivity, but negative effect on the reactivity (entries 16 and 17). Table 3. Scope of the Rh-catalyzed Asymmetric Addition of Arylboronic Acids to Unsaturated Esters.a

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DOI: 10.1039/C3OB41342J

calcd for C23H22O3Na [M + Na]+ 369.1467, found 369.1458.

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Methyl 3-(2-methoxyphenyl)-3-phenylpropanoate (6e). White solid, mp 50–51 °C, 62 mg, 76% yield, 89% ee; [α]23D = –17.3 (c = 1.2, CHCl3); HPLC: Chiracel OD-H column, detected at 230 nm, n-hexane/i-propanol = 80/20, flow = 1.0 mL/min (49 bar), tR = 5.6 min (major) and 14.5 min (minor); 1 H NMR (400 MHz, CDCl3): δ 7.29–7.20 (m, 4H), 7.20–7.10 (m, 3H), 6.92–6.85 (m, 1H), 6.82 (d, J = 7.9 Hz, 1H), 4.94 (t, J = 8.0 Hz, 1H), 3.75 (s, 3H), 3.55 (s, 3H), 3.14–2.92 (m, 2H); 13 C NMR (100 MHz, CDCl3): δ 172.6, 156.9, 143.3, 132.0, 128.4, 128.0, 127.8, 127.7, 126.3, 120.6, 110.9, 55.5, 51.6, 40.5, 39.5; HRMS (ESI, m/z) calcd for C17H18O3Na [M + Na] + 293.1154, found 293.1157. Methyl 3-phenyl-3-p-tolylpropanoate (6f). 18 Colorless oil, 70 mg, 92% yield, 86% ee; [α]24D = 1.4 (c = 1.4, CHCl3); HPLC: Chiracel OD-H column, detected at 230 nm, nhexane/i-propanol = 80/20, flow = 1.0 mL/min (49 bar), tR = 4.7 min (minor) and 6.3 min (major); 1H NMR (400 MHz, CDCl3): δ 7.29–7.19 (m, 4H), 7.18–7.13 (m, 1H), 7.09 (q, J = 8.1 Hz, 4H), 4.52 (t, J = 8.0 Hz, 1H), 3.55 (s, 3H), 3.03 (d, J = 8.0 Hz, 2H), 2.27 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 172.4, 143.8, 140.6, 136.1, 129.3, 128.6, 127.7, 127.6, 126.5, 51.7, 46.7, 40.7, 21.1; HRMS (ESI, m/z) calcd for C17H18O2Na [M + Na]+ 277.1204, found 277.1201. Methyl 3-(4-tert-butylphenyl)-3-phenylpropanoate (6g). White solid, mp 49–50 °C, 81 mg, 91% yield, 89% ee; [α]24D = 3.9 (c = 1.4, CHCl3); HPLC: Chiracel OD-H column, detected at 230 nm, n-hexane/i-propanol = 90/10, flow = 1.0 mL/min (44 bar), tR = 4.5 min (minor) and 6.0 min (major); 1 H NMR (400 MHz, CDCl3): δ 7.26 (q, J = 8.1 Hz, 6H), 7.16 (t, J = 8.3 Hz, 3H), 4.53 (t, J = 7.8 Hz, 1H), 3.56 (s, 3H), 3.05 (d, J = 7.9 Hz, 2H), 1.27 (s, 9H); 13C NMR (100 MHz, CDCl3): δ 172.5, 149.3, 143.8, 140.5, 128.6, 127.8, 127.3, 126.6, 125.6, 51.7, 46.7, 40.8, 34.5, 31.5; HRMS (ESI, m/z) calcd for C20H24O2Na [M + Na]+ 319.1674, found 319.1678. Methyl 3-(naphthalen-1-yl)-3-phenylpropanoate (6h).18 Colorless oil, 52 mg, 60% yield, 83% ee; [α]24D = 10.0 (c = 1.1, CHCl3); HPLC: Chiracel OD-H column, detected at 230 nm, n-hexane/i-propanol = 90/10, flow = 1.0 mL/min (44 bar), tR = 10.0 min (major) and 15.9 min (minor); 1H NMR (400 MHz, CDCl3): δ 8.13 (d, J = 7.2 Hz, 1H), 7.78 (dd, J = 34.2, 7.2 Hz, 2H), 7.53–7.05 (m, 9H), 5.38 (t, J = 7.1 Hz, 1H), 3.60 (d, J = 17.5 Hz, 3H), 3.27–3.03 (m, 2H); 13C NMR (100 MHz, CDCl3): δ 172.5, 143.5, 139.0, 134.2, 131.6, 128.9, 128.7, 127.9, 127.6, 126.7, 126.3, 125.7, 125.4, 124.3, 123.9, 51.9, 42.7, 41.3; HRMS (ESI, m/z) calcd for C20H18O2Na [M + Na] + 313.1204, found 313.1206. Methyl 3-(naphthalen-2-yl)-3-phenylpropanoate (6i). White solid, mp 76–78 °C, 86 mg, 99% yield, 79% ee; [α]24D = 22.1 (c = 1.7, CHCl3); HPLC: Chiracel OD-H column, detected at 230 nm, n-hexane/i-propanol = 90/10, flow = 1.0 mL/min (44 bar), tR = 8.2 min (minor) and 12.7 min (major); 1H NMR (400 MHz, CDCl3): δ 7.74 (dd, J = 21.2, 10.4 Hz, 4H), 7.51– 7.04 (m, 8H), 4.72 (t, J = 7.4 Hz, 1H), 3.54 (s, 3H), 3.27–2.99 (m, 2H); 13C NMR (100 MHz, CDCl3): δ 172.3, 143.4, 140.9, 133.6, 132.4, 128.7, 128.4, 127.9, 127.7, 126.7, 126.6, 126.2, 4 | [journal], [year], [vol], 00–00

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Methyl 3-(3,4-dimethoxyphenyl)-3-phenylpropanoate (6j). Colorless oil, 86 mg, 95% yield, 88% ee; [α]24D = –2.2 (c = 1.4, CHCl3); HPLC: Chiracel OD-H column, detected at 230 nm, n-hexane/i-propanol = 95/5, flow = 1.0 mL/min (47 bar), tR = 7.9 min (minor) and 9.8 min (major); 1H NMR (400 MHz, CDCl3): δ 7.35–7.07 (m, 5H), 6.76 (d, J = 19.6 Hz, 3H), 4.51 (t, J = 7.7 Hz, 1H), 3.81 (d, J = 4.7 Hz, 6H), 3.57 (s, 3H), 3.03 (d, J = 7.9 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 172.3, 149.0, 147.8, 143.8, 136.2, 128.6, 127.6, 126.6, 119.5, 111.5, 111.3, 55.9, 51.7, 46.6, 40.9; HRMS (ESI, m/z) calcd for C18H20O4Na [M + Na]+ 323.1259, found 323.1263. Methyl 3-(4-fluorophenyl)-3-phenylpropanoate (6k). Colorless oil, 72 mg, 93% yield, 89% ee; [α]24D = –3.6 (c = 1.3, CHCl3); HPLC: Chiracel OD-H column, detected at 230 nm, n-hexane/i-propanol = 90/10, flow = 1.0 mL/min (44 bar), tR = 5.6 min (minor) and 7.9 min (major); 1H NMR (400 MHz, CDCl3): δ 7.34–7.12 (m, 7H), 6.95 (dd, J = 11.9, 5.4 Hz, 2H), 4.54 (t, J = 7.9 Hz, 1H), 3.57 (s, 3H), 3.03 (d, J = 8.2 Hz, 2H); 13 C NMR (100 MHz, CDCl3): δ 172.2, 162.9, 160.4, 143.4, 139.3 (d, J = 3.3 Hz), 129.3, 129.2, 128.8, 127.6, 126.8, 115.6, 115.4, 77.5, 77.2, 76.8, 51.8, 46.3, 40.8; HRMS (ESI, m/z) calcd for C16H15FO2Na [M + Na] + 281.0954, found 281.0952. Methyl 3-(4-chlorophenyl)-3-phenylpropanoate (6l). White solid, mp 32–34 °C, 72 mg, 88% yield, 89% ee; [α]24D = –2.0 (c = 1.2, CHCl3); HPLC: Chiracel OD-H column, detected at 230 nm, n-hexane/i-propanol = 90/10, flow = 1.0 mL/min (44 bar), tR = 5.9 min (minor) and 8.5 min (major); 1H NMR (400 MHz, CDCl3): δ 7.22 (ddt, J = 21.5, 14.6, 7.2 Hz, 9H), 4.53 (t, J = 7.8 Hz, 1H), 3.57 (s, 3H), 3.03 (d, J = 7.8 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 172.1, 143.1, 142.1, 132.5, 129.2, 128.8, 127.6, 126.9, 51.8, 46.4, 40.5; HRMS (ESI, m/z) calcd for C16H15ClO2Na [M + Na]+ 297.0658, found 297.0653. Methyl 3-(4-bromophenyl)-3-phenylpropanoate (6m). White solid, mp 55–56 °C, 70 mg, 73% yield, 91% ee; [α]24D = –1.3 (c = 1.0, CHCl3); HPLC: Chiracel OD-H column, detected at 230 nm, n-hexane/i-propanol = 90/10, flow = 1.0 mL/min (44 bar), tR = 6.2 min (minor) and 8.9 min (major); 1 H NMR (400 MHz, CDCl3): δ 7.39 (d, J = 8.1 Hz, 2H), 7.27 (t, J = 7.2 Hz, 2H), 7.19 (d, J = 5.5 Hz, 3H), 7.10 (d, J = 8.0 Hz, 2H), 4.51 (t, J = 7.8 Hz, 1H), 3.58 (s, 3H), 3.02 (d, J = 7.9 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 172.1, 143.0, 142.6, 131.8, 129.6, 128.8, 127.7, 126.9, 120.6, 51.9, 46.5, 40.5; HRMS (ESI, m/z) calcd for C16H15BrO2Na [M + Na]+ 341.0153, found 341.0156. Methyl 3-phenyl-3-(4-(trifluoromethyl)phenyl)propanoate (6n). Colorless oil, 85 mg, 92% yield, 91% ee; [α]24D = –0.9 (c = 1.5, CHCl3); HPLC: Chiracel OD-H column, detected at 230 nm, n-hexane/i-propanol = 90/10, flow = 1.0 mL/min (44 bar), tR = 5.8 min (minor) and 7.9 min (major); 1H NMR (400 MHz, CDCl3): δ 7.53 (d, J = 8.2 Hz, 2H), 7.35 (d, J = 8.1 Hz, 2H), 7.28 (dd, J = 9.4, 5.8 Hz, 2H), 7.20 (dd, J = 9.9, 4.4 Hz, 3H), 4.72–4.53 (m, 1H), 3.58 (s, 3H), 3.07 (d, J = 8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 171.9, 147.7, 142.7, 129.2, 128.9, 128.2, 127.7, 127.1, 125.7 (q, J = 3.8 Hz), 122.9, 51.9, 46.9,

This journal is © The Royal Society of Chemistry [The year]

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125.7, 51.8, 47.1, 40.6; HRMS (ESI, m/z) calcd for C20H18O2Na [M + Na]+ 313.1204, found 313.1200.

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Methyl 3-(3,4-dimethoxyphenyl)-3-(4methoxyphenyl)propanoate (6o). Colorless oil, 82 mg, 83% yield, 90% ee; [α]24D = –1.6 (c = 1.6, CHCl3); HPLC: Chiracel AD-H column, detected at 230 nm, n-hexane/i-propanol = 95/5, flow = 1.0 mL/min (44 bar), tR = 26.5 min (major) and 28.5 min (minor); 1H NMR (400 MHz, CDCl 3): δ 7.14 (d, J = 6.8 Hz, 2H), 6.78 (dd, J = 29.6, 15.9 Hz, 5H), 4.45 (d, J = 7.5 Hz, 1H), 3.82 (d, J = 4.0 Hz, 6H), 3.76 (s, 3H), 3.58 (s, 3H), 3.00 (d, J = 7.3 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 172.5, 158.1, 148.9, 147.6, 136.6, 135.9, 128.6, 119.3, 114.0, 111.3, 55.9, 55.3, 51.7, 45.9, 41.2; HRMS (ESI, m/z) calcd for C19H22O5Na [M + Na]+ 353.1365, found 353.1364. Methyl 3-(4-fluorophenyl)-3-(4-methoxyphenyl) propanoate (6p). Colorless oil, 73mg, 85% yield, 90% ee; [α]24D = 1.1 (c = 1.3, CHCl3); HPLC: Chiracel OD-H column, detected at 230 nm, n-hexane/i-propanol = 95/5, flow = 1.0 mL/min (47 bar), tR = 7.9 min (major) and 8.7 min (minor); 1 H NMR (400 MHz, CDCl3): δ 7.14 (dd, J = 18.4, 7.9 Hz, 4H), 7.04–6.74 (m, 4H), 4.50 (d, J = 5.9 Hz, 1H), 3.74 (s, 3H), 3.56 (s, 3H), 2.99 (d, J = 7.6 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 172.2, 162.8, 160.3, 158.4, 139.7, 135.5, 129.1, 129.1, 128.6, 115.5, 114.9, 114.1, 55.2, 51.7, 45.5, 40.9; HRMS (ESI, m/z) calcd for C17H17FO3Na [M + Na] + 311.1059, found 311.1052. Methyl 3-(4-fluorophenyl)-3-(4(trifluoromethyl)phenyl)propanoate (6q). Colorless oil, 61 mg, 62% yield, 90% ee; [α]23D = 1.5 (c = 1.0, CHCl3); HPLC: Chiracel AD-H column, detected at 230 nm, n-hexane/ipropanol = 95/5, flow = 1.0 mL/min (44 bar), tR = 6.3 min (minor) and 6.7 min (major); 1H NMR (400 MHz, CDCl 3): δ 7.54 (d, J = 6.8 Hz, 2H), 7.34 (s, 2H), 7.18 (s, 2H), 6.99 (d, J = 6.8 Hz, 2H), 4.63 (t, J = 13.6 Hz, 1H), 3.60 (s, 3H), 3.08 (t, J = 20.1 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 171.8, 163.1, 160.9, 147.4, 138.4, 129.3 (d, J = 7.9 Hz), 128.1, 126.0–125.6 (m), 115.9, 115.7, 51.9, 46.2, 40.5; HRMS (ESI, m/z) calcd for C17H14F 4O2Na [M+Na] + 349.0828, found 349.0826.

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Financial support from the National Basic Research Program of China (2010CB833300) and the National Natural Science Foundation of China (21172218) are gratefully acknowledged.

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(1) (a) Transition Metals for Organic Synthesis, (Eds.: M. Beller, C. Bolm,), Wiley-VCH, Weinheim, 2004; (b) Multimetallic Catalysts in Organic Synthesis, (Eds.: M. Shibasaki, Y.Yamamoto,), Wiley-VCH, Weinheim, 2004; (c) Transition Metal Catalysed Reactions (Eds.: S. Murahashi, S. G. Davies,), Blackwell Science, Oxford, 1999. (2) For selected reviews, see: (a) T. Hayashi, Synlett, 2001, 879; (b) K. Fagnou and M. Lautens, Chem. Rev., 2003, 103, 169; (c) T. Hayashi and K. Yamasaki, Chem. Rev., 2003, 103, 2829; (d) T. Hayashi and K. Yoshida, in Modern RhodiumThis journal is © The Royal Society of Chemistry [The year]

(5) J .Chen, J. M. Chen, F. Lang, X. Y. Zhang, L. F.Cun, J. Zhu, J. G. Deng and J. Liao, J. Am. Chem. Soc., 2010, 132, 45, 52. (6) F. Xue, X. C. Li and B. S.Wan, J. Org. Chem., 2011, 76, 7256.

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(7) F. Xue, D. P.Wang, X. C. Li and B. S. Wan, J. Org. Chem., 2012, 77, 3081. (8) (a) W. Y. Qi, T. S. Zhu and M. H. Xu, Org. Lett., 2011, 13, 3410; (b) G. H. Chen, J. Y. Gui, L. C. Li and J. Liao, Angew. Chem. Int. Ed., 2011, 50, 7681.

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(3) For selected documents, see: (a) Z. Q. Wang, C. G. Feng, M. H. Xu and G. Q. Lin, J. Am. Chem. Soc., 2007, 129, 5336. and references therein; (b) Z. P. Cao and H. F. Du, Org. Lett., 2010, 12, 2602; (c) R. Shintani, M. Takeda, T. Tsuji and T. Hayashi, J. Am. Chem. Soc., 2010, 132, 13168; (d) R. Shintani, M. Takeda, Y. T. Soh, I. Tomoaki and T. Hayashi, Org. Lett., 2011, 13, 2977; (e) Z. Cui, H. J. Yu, R. F. Yang, W. Y. Gao, C. G. Feng and G. Q. Lin, J. Am. Chem. Soc., 2011, 133, 12394. (4) B. T. Hahn, F. Tewes, R. Fröhlich and F. Glorius, Angew. Chem., Int. Ed., 2010, 49, 1143.

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Catalyzed Organic Reactions, (Eds.: P. A. Evans,), WileyVCH, Weinheim, 2004, pp. 55–78; (e) J. Christoffers, G. Koripelly, A. Rosiak, and M. Rössle, Synthesis, 2007, 1279.

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(9) For selected documents, see: (a) T. Thaler, L. N. Guo, A. K. Steib, M. Raducan, K. Karaghiosoff, P. Mayer and P. Knochel, Org. Lett., 2011, 13, 3182; (b) S. S. Jin, H. Wang and M. H. Xu, Chem. Commun., 2011, 47, 7230; (c) X. Q. Feng, Y. Z. Wang, B. B. Wei, J. Yang and H. F. Du, Org. Lett., 2011, 13, 3300; (d) Y. Z. Wang, X. Q. Feng and H. F. Du, Org. Lett., 2011, 13, 4954; (e) T. S. Zhu, S. S. Jin and Xu, M. H. Angew. Chem. Int. Ed., 2012, 51, 780; (f) X. Q. Feng, Y. Z. Nie, J. Yang and H. F. Du, Org. Lett., 2012, 14, 624; (g) P. Tian, H. Q. Dong and G. Q. Lin, ACS Catalysis, 2012, 2, 95; (h) D. W. Low, G. Pattison, M. D. Wieczysty, G. H. Churchill and H. W. Lam, Org. Lett., 2012, 14, 2548; (i) Z. Q. Liu, X. Q. Feng and H. F. Du, Org. Lett., 2012, 14, 3154; (j) T. S. Zhu, J. P. Chen and M. H. Xu, Chem. Eur. J., 2013, 19, 865; (k) H. Wang, T. Jiao and M. H. Xu, J. Am. Chem. Soc., 2013, 135, 971. (10) For selected documents, see: (a) T. Hayashi, K. Ueyama, N.Tokunaga and K. Yoshida, J. Am. Chem. Soc., 2003, 125, 11508; (b) C. Fischer, C. Defieber, T. Suzuki and E. M. Carreira, J. Am. Chem. Soc., 2004, 126, 1628; (c) W. L. Duan, H. Iwamura, R. Shintania and T.Hayashi, J. Am. Chem. Soc., 2007, 129, 2130; (d) C. G. Feng, Z. Q. Wang, C. Shao, M. H. Xu and G. Q. Lin, Org. Lett., 2008, 10, 4101; (e) T. Gendrineau, O. Chuzel, H. Eijsberg, J. P. Genet and S. Darses, Angew. Chem., Int. Ed., 2008, 47, 7669; (f) K. Okamoto, T. Hayashi and V. H. Rawal, Org. Lett., 2008, 10, 4387; (g) Q. A. Chen, X. Dong, M. W. Chen,; D. S. Wang, Y. G. Zhou and Y. X. Li, Org. Lett., 2010, 12, 1928. (h) B. T. Hahn, F. Tewes, R. Fröhlich and F. Glorius, Angew. Chem. Int. Ed., 2010, 49, 1143. [journal], [year], [vol], 00–00 | 5

Organic & Biomolecular Chemistry Accepted Manuscript

40.3; HRMS (ESI, m/z) calcd for C17H15F3O2Na [M + Na]+ 331.0922, found 331.0929.

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(11) For selected documents, see: (a) R. Mariz, X. J. Luan, M. Gatti, A. Linden and R. Dorta, J. Am. Chem. Soc., 2008, 130, 2172; (b) J. Bürgi, R. Mariz, M. Gatti, E. Drinkel, X. J. Luan, S. Blumentritt, A. Linden and R. Dorta, Angew. Chem. Int. Ed., 2009, 48, 2768; (c) R. Mariz, A. Poater, M. Gatti, E. Drinkel, J. J. Bürgi, X. J. Luan, S. Blumentritt, A. Linden, L. Cavallo and R. Dorta, Chem. −Eur. J., 2010, 16, 14335; (d) X. C. Hu, M. Y. Zhuang, Z. P. Cao and H. F. Du, Org. Lett., 2009, 11, 4744; (e) R. Jana and J. A. Tunge, Org. Lett., 2009, 11, 971; (f) J. Chen, J. M. Chen, F. Lang, X. Y. Zhang, L. F. Cun, J. Zhu, J. G. Deng and J. Liao, J. Am. Chem. Soc., 2010, 132, 4552. (12) C. Defieber, J. F. Paquin, S. Serna and E. M. Carreira, Org. Lett., 2004, 6, 3873.

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(13) T. Itoh, T. Mase, T. Nishikata, T. Iyama, H. Tachikawa, Y. Kobayashi, Y. Yamamoto and N. Miyaura, Tetrahedron, 2006, 62, 9610. (14) J. F. Paquin, C. R. J. Stephenson, C. Defieber and E. M. Carreira, Org. Lett., 2005, 7, 3821.

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(15) S. So1rgel, N. Tokunaga, K. Sasaki, K. Okamoto and T. Hayashi, Org. Lett., 2008, 10, 589. (16) M. Lautens, J. Mancuso and H. Crover, Synthesis, 2004, 2006.

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(17) A. I. Meyers, R. K. Smith and C. E. Whitten, J. Org. Chem., 1979, 44, 2250. (18) Y. Arai, K. Udea, J. H. Xie and Y. Masaki, Chem. Pharm. Bull., 2001, 49, 1609.

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Chiral olefin-sulfoxide as ligands for rhodium-catalyzed asymmetric conjugate addition of arylboronic acids to unsaturated esters.

An efficient rhodium/olefin-sulfoxide catalyzed asymmetric conjugate addition of organoboronic acids to various unsaturated esters has been developed,...
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