Ir-Catalyzed Intermolecular Asymmetric Allylic Alkylation of β-Tetralones

9 hours ago - The Supporting Information is available free of charge on the ACS ... Experimental procedures and analysis data for all new compounds (P...
1 downloads 0 Views 726KB Size
Download PDF
Article Cite This: Organometallics XXXX, XXX, XXX−XXX

pubs.acs.org/Organometallics

Ir-Catalyzed Intermolecular Asymmetric Allylic Alkylation of β‑Tetralones Dong-Song Zheng,† Zheng-Le Zhao,† Qing Gu,* and Shu-Li You* State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, People’s Republic of China

Downloaded via NOTTINGHAM TRENT UNIV on August 28, 2019 at 01:09:29 (UTC). See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

S Supporting Information *

ABSTRACT: β-Tetralones are useful synthetic intermediates and can act as precursors of β-naphthols. Herein, Ir-catalyzed intermolecular asymmetric alkylation of substituted β-tetralones has been realized. In the presence of an Ir complex, derived from 2 mol % of [Ir(cod)Cl]2 and 4 mol % of the Alexakis ligand, asymmetric allylic alkylation reactions of various β-tetralones and allyl carbonates proceeded smoothly in good to excellent yields with excellent enantioselectivity. The reaction provides an efficient synthesis of highly enantioenriched tetralones and β-naphthols.

■

INTRODUCTION Ir-catalyzed asymmetric allylic substitution reactions have been well developed in the last three decades, providing reliable synthesis of chiral allylic stereocenters in high enantioselectivity.1−3 Among the nucleophiles developed, aromatic compounds are found to be compatible ones, and efficient C−C formation results via a Friedel−Crafts type allylic alkylation. However, asymmetric allylic alkylation of phenols and naphthols by forming C−C bonds is challenging since the reaction generally proceeds with O-alkylation, forming a C−O bond (Scheme 1).4 Previous successful examples are mainly

might proceed in high stereoselectivity and the products obtained should be able to be converted to enantioenriched βnaphthols. In this paper, we report our results on Ir-catalyzed asymmetric allylic alkylation of β-tetralones. The interconversion of alkylated β-tetralone product to the corresponding βnaphthol has also been demonstrated.

■

RESULTS AND DISCUSSION At the outset of our study, we chose methyl cinnamyl carbonate (2a) as the electrophile to test the allylic substitution reaction of β-tetralone (1a). In the presence of an iridium catalyst prepared from [Ir(cod)Cl]2 (2 mol %) and the (S,S,Sa)-Feringa ligand L1 (4 mol %),9 the allylic alkylation reaction of β-tetralone with t-BuOLi (100 mol %) as the base in CH2Cl2 proceeded smoothly to give a mixture of alkylated diastereoisomers 3a (dr = 1:1). By conversion of the ketone moiety to a silyl enol ether, 3aa was prepared with 90% ee in 73% yield over two steps (Scheme 2). Encouraged by these preliminary results, we further screened a series of chiral phosphoramidite ligands (L2−L6). The results are summarized in Scheme 3. The reaction with the (S,S,Sa)-Alexakis ligand (L2)10 gave 3aa in excellent yield (93%) with slightly increased ee (92%). A trace amount of 3aa was obtained in the presence of L3. The reactions with THQphos (L4) and BHPphos (L5)11 only led to moderate yields and ee values (Scheme 3: L4, 56% yield, 62% ee; L5,

Scheme 1. Asymmetric Allylic Alkylation Reaction of Naphthol and β-Tetralone

based on intramolecular design to overcome the competition of O-alkylation.5,6 There are only sporadic examples of intermolecular C-allylation reactions of naphthols.7 On the other hand, β-tetralones are important synthetic intermediates and can act as the precursors of β-naphthols.8 We envisaged that Ir-catalyzed asymmetric allylic alkylation of β-tetralones © XXXX American Chemical Society

Special Issue: Asymmetric Synthesis Enabled by Organometallic Complexes Received: June 20, 2019

A

DOI: 10.1021/acs.organomet.9b00416 Organometallics XXXX, XXX, XXX−XXX

Article

Organometallics Table 1. Screening of Solvents and Basesa

Scheme 2. Preliminary Attempt of Ir-Catalyzed Asymmetric Allylic Alkylation of β-Tetralone

Scheme 3. Screening of the Ligands

entry

base

solvent

yield/%b

ee/%c

1 2 3 4 5 6 7 8 9 10 11 12

t-BuOLi t-BuOLi t-BuOLi t-BuOLi t-BuOLi t-BuONa t-BuOK (t-BuO)2Mg Cs2CO3 DMAP DABCO none

DCM toluene 1,4-dioxane THF Et2O Et2O Et2O Et2O Et2O Et2O Et2O Et2O

93 64 96 93 97 20/1 [Phenomenex lux 5 μ Cellulose-1 (0.46 cm × 25 cm); methanol/water = 90/10; flow rate 0.7 mL/min; detection wavelength 254 nm; tR = 28.76 (major), 27.10 (minor) min]. [α]D20 = −45.6 (c = 2.5, CHCl3). 1H NMR (300 MHz, CDCl3): δ 7.24−7.19 (m, 2H), 7.08−7.00 (m, 3H), 6.94−6.84 (m, 3H), 6.48−6.35 (m, 1H), 5.29 (d, J = 4.5 Hz, 1H), 5.22 (d, J = 14.4 Hz, 1H), 5.21 (d, J = 12.0 Hz, 1H), 2.96−2.80 (m, 2H), 2.65−2.54 (m, 1H), 2.50−2.40 (m, 3H), 1.86−1.77 (m, 1H), 0.91 (s, 9H), 0.89 (s, 6H), 0.19 (s, 3H), 0.15 (s, 3H). 13C NMR (75 MHz, CDCl3): δ 151.7, 140.1, 139.1, 135.6, 134.1, 129.1, 127.4, 127.1, 126.0, 125.3, 124.4, 116.9, 116.8, 45.3, 45.1, 30.5, 29.8, 29.6, 26.0, 22.7, 22.6, 18.4, −3.1. IR (film): νmax (cm−1) 3061, 2957, 2887, 2859, 1626, 1602, 1507, 1467, 1363, 1336, 1256, 1193, 1159, 1092, 1001, 964, 885, 829, 781, 755, 723, 677. ESIMS (m/z): exact mass calcd for C29H41OSi [M + H]+, 433.2921; found, 433.2919.

Scheme 4. Aromatization of Substituted Tetralone

meric mixture 3a was hydrogenated under 1 atm of H2 in the presence of 10% Pd/C. The aromatization of 4a with TBSOTf (20 mol %) and NBS (100 mol %) then afforded C1-alkylated 2-naphthol 5a in 90% yield and without erosion of enantioselectivity (93% ee).8a The absolute configuration of 5a was assigned as S by comparing the sign of the optical rotation with that of (R)-5a obtained from the known method (for details, see the Supporting Information).7e A proposed mechanism13 as depicted in Scheme 5 starts with the active metallacyclic iridium phosphoramidite catalyst Scheme 5. Proposed Catalytic Cycle

(I) generated from [Ir(COD)Cl]2 and L by nPrNH2 activation. Irreversible anti-nucleophilic attack of β-tetralone on the πallyliridium intermediate (II), which is generated after oxidative addition of the allylic carbonate to I, occurs to afford Ir species III. The final product is obtained with regeneration of the active species after dissociation to finish the catalytic cycle. This alkylation is considered to be an “outersphere” process, since the absolute configuration of the product is consistent with the mechanism proposed by Hartwig and co-workers.13c

■

CONCLUSION In summary, we have developed an efficient iridium-catalyzed intermolecular asymmetric allylic alkylation reaction of βtetralones under mild conditions. The reaction displays rather general substrate scope and tolerates a variety of functional groups. The tetralone moiety in the product can be further oxidized to naphthol without affecting the enantioselectivity of the stereocenter. Therefore, the method here offers an alternative route for Friedel−Crafts type allylic alkylation of β-naphthols.

■

EXPERIMENTAL SECTION

General Procedure for Ir-Catalyzed Intermolecular Asymmetric Allylic Alkylation of β-Tetralone. A flame-dried Schlenk tube was cooled to room temperature and filled with argon. In this flask were placed [Ir(cod)Cl]2 (5.7 mg, 0.01 mmol, 2 mol %), C

DOI: 10.1021/acs.organomet.9b00416 Organometallics XXXX, XXX, XXX−XXX

Article

Organometallics Compound (S)-3ad: colorless oil, 192.3 mg, 93% yield, 96% ee. b/l > 20/1 [Phenomenex lux 5 μ Cellulose-1 (0.46 cm × 25 cm); methanol/water = 90/10; flow rate 0.7 mL/min; detection wavelength 254 nm; tR = 22.94 (major), 20.37 (minor) min]. [α]D20 = −66.5 (c = 2.0, CHCl3). 1H NMR (400 MHz, CDCl3): δ 7.25−7.20 (m, 4H), 7.08−7.06 (m, 1H), 6.96−6.89 (m, 2H), 6.78 (dd, J = 7.2, 2.0 Hz, 1H), 6.41−6.32 (m, 1H), 5.26−5.18 (m, 3H), 2.96−2.80 (m, 2H), 2.60−2.39 (m, 2H), 0.88 (s, 9H), 0.18 (s, 3H), 0.13 (s, 3H). 13C NMR (75 MHz, CDCl3): δ 152.1, 141.6, 138.3, 135.1, 134.0, 131.6, 129.1, 128.5, 127.2, 126.0, 125.0, 124.6, 117.7, 116.2, 44.8, 29.7, 29.5, 26.0, 25.9, 18.4, −3.1, −3.1. IR (film): νmax (cm−1) 3415, 3068, 3024, 2952, 2928, 2856, 1710, 1635, 1596, 1490, 1405, 1326, 1258, 1164, 1091, 1014, 968, 922, 832, 747, 643. ESI-MS (m/z): exact mass calcd for C25H32OClSi [M + H]+, 411.1905; found, 411.1905. Compound (S)-3ae: colorless oil, 216.4 mg, 95% yield, 96% ee. b/l > 20/1 [Daicel Chiralcel OD-H (0.46 cm × 25 cm); CO2/2-propanol = 92/8; flow rate 1.3 mL/min; detection wavelength 230 nm; tR = 9.75 (major), 9.34 (minor) min]. [α]D20 = −84.9 (c = 0.5, CHCl3). 1 H NMR (300 MHz, CDCl3): δ 7.36 (d, J = 8.4 Hz, 2H), 7.18 (d, J = 8.7 Hz, 2H), 7.08−7.05 (m, 1H), 6.96−6.90 (m, 2H), 6.80−6.76 (m, 1H), 6.43−6.30 (m, 1H), 5.24−5.17 (m, 3H), 2.98−2.80 (m, 2H), 2.61−2.37 (m, 2H), 0.88 (s, 9H), 0.18 (s, 3H), 0.14 (s, 3H). 13C NMR (75 MHz, CDCl3): δ 152.1, 142.2, 138.2, 135.1, 134.1, 131.4, 129.6, 127.3, 126.1, 125.0, 124.6, 119.8, 117.8, 116.2, 44.9, 29.8, 29.5, 26.0, 18.5, −3.0, −3.0. IR (film): νmax (cm−1) 3072, 3019, 2954, 2931, 2888, 2858, 1626, 1568, 1485, 1468, 1362, 1335, 1257, 1195, 1160, 1074, 1005, 968, 917, 892, 823, 781, 759, 723, 676. ESI-MS (m/z): exact mass calcd for C25H32BrOSi [M + H]+, 455.1400; found, 455.1401. Compound (S)-3af: colorless oil, 215.5 mg, 97% yield, 95% ee. b/l > 20/1 [Daicel Chiralpak OD-H (0.46 cm × 25 cm); CO2/2propanol = 98/2; flow rate 1.3 mL/min; detection wavelength 214 nm; tR = 10.98 (major), 10.31 (minor) min]. [α]D20 = −52.2 (c = 0.5, CHCl3). 1H NMR (300 MHz, CDCl3): δ 7.56 (d, J = 8.7 Hz, 2H), 7.48 (d, J = 8.1 Hz, 2H), 7.10−7.06 (m, 1H), 6.95−6.91 (m, 2H), 6.79−6.75 (m, 1H), 6.46−6.34 (m, 1H), 5.37 (d, J = 7.8 Hz, 1H), 5.31 (d, J = 9.0 Hz, 1H), 5.29 (d, J = 18.9 Hz, 1H), 3.00−2.82 (m, 2H), 2.63−2.42 (m, 2H), 0.87 (s, 9H), 0.18 (s, 3H), 0.15 (s, 3H). 13C NMR (75 MHz, CDCl3): δ 152.3, 147.5, 147.5, 137.8, 135.1, 134.0, 128.2 (q, J = 32.3 Hz), 128.0, 127.3, 126.1, 125.4 (q, J = 3.7 Hz), 124.7 (q, J = 7.4 Hz), 124.7 (q, J = 270.5 Hz), 118.1, 116.0, 45.4, 30.0, 29.5, 25.9, 18.4, −3.0, −3.1. 19F NMR (282 MHz): δ −62.5. IR (film): νmax (cm−1) 3068, 2954, 2934, 2891, 2861, 1622, 1566, 1486, 1411, 1364, 1327, 1258, 1198, 1158, 1118, 1067, 1004, 971, 920, 894, 824, 775, 757, 720, 672, 620. ESI-MS (m/z): exact mass calcd for C26H32F3OSi [M + H]+, 445.2169; found, 445.2168. Compound (S)-3ag: colorless, 188.7 mg, 96% yield, 93% ee. b/l > 20/1 [Phenomenex lux 5 μ Cellulose-1 (0.46 cm × 25 cm); methol/ water = 90/10; flow rate 0.7 mL/min; detection wavelength 254 nm; tR = 17.77 (major), 16.04 (minor) min]. [α]D20 = −44.4 (c = 2.0, CHCl3). 1H NMR (300 MHz, CDCl3): δ 7.24−7.16 (m, 1H), 7.11− 7.01 (m, 3H), 6.94−6.91 (m, 2H), 6.86−6.81 (m, 2H), 6.45−6.32 (m, 1H), 5.29−5.19 (m, 3H), 2.98−2.78 (m, 2H), 2.62−2.37 (m, 2H), 0.88 (s, 9H), 0.18 (s, 3H), 0.15 (s, 3H). 13C NMR (75 MHz, CDCl3): δ 163.4 (d, J = 242.9 Hz), 152.1, 146.1 (d, J = 6.9 Hz), 138.1, 135.2, 134.1, 129.8 (d, J = 8.1 Hz), 127.3, 126.1, 124.9, 124.6, 123.3 (d, J = 2.8 Hz), 117.9, 116.2, 114.7 (d, J = 21.9 Hz), 112.8 (d, J = 21.3 Hz), 45.3, 29.8, 29.5, 26.0, 18.5, −2.9, −3.0. 19F NMR (282 MHz): δ −114.2 (m). IR (film): νmax (cm−1) 2954, 2931, 2889, 2857, 1627, 1587, 1485, 1468, 1444, 1363, 1257, 1197, 1069, 1002, 983, 867, 832, 778, 754, 683. ESI-MS (m/z): exact mass calcd for C25H32FOSi [M + H]+, 395.2201; found, 395.2204. Compound (S)-3ah: colorless oil, 188.9 mg, 91% yield, 98% ee. b/l > 20/1 [Daicel Chiralcel OD-H (0.46 cm × 25 cm); CO2/2-propanol = 97/3; flow rate 1.3 mL/min; detection wavelength 230 nm; tR = 12.05 (major), 12.97 (minor) min]. [α]D20 = −50.8 (c = 1.0, CHCl3). 1 H NMR (400 MHz, CDCl3): δ 7.31 (s, 1H), 7.18−7.07 (m, 4H), 6.97−6.91 (m, 2H), 6.81−6.79 (m, 1H), 6.42−6.33 (m, 1H), 5.24− 5.19 (m, 3H), 2.97−2.80 (m, 2H), 2.61−2.39 (m, 2H), 0.88 (s, 9H), 0.18 (s, 3H), 0.15 (s, 3H). 13C NMR (75 MHz, CDCl3): δ 152.2,

145.5, 138.1, 135.3, 134.5, 134.1, 129.8, 127.9, 127.4, 126.3, 126.3, 126.0, 124.9, 124.8, 118.0, 116.2, 45.4, 29.9, 29.6, 26.2, 26.1, 18.5, −2.8, −2.9. IR (film): νmax (cm−1) 3066, 3018, 2953, 2931, 2888, 2858, 1626, 1594, 1569, 1470, 1422, 1362, 1335, 1256, 1193, 1160, 1090, 1002, 968, 917, 829, 780, 761, 735, 679. ESI-MS (m/z): exact mass calcd for C25H32ClOSi [M + H]+, 411.1905; found, 411.1901. Compound (S)-3ai: colorless oil, 213.1 mg, 94% yield, 95% ee. b/l > 20/1 [Daicel Chiralpak AD-H (0.46 cm × 25 cm); CO2/2-propanol = 95/5; flow rate 1.3 mL/min; detection wavelength 230 nm; tR = 5.80 (major), 6.25 (minor) min]. [α]D20 = −58.8 (c = 1.0, CHCl3). 1 H NMR (300 MHz, CDCl3): δ 7.48 (s, 1H), 7.29−7.18 (m, 2H), 7.12−7.05 (m, 2H), 6.95−6.91 (m, 2H), 6.82−6.78 (m, 1H), 6.43− 6.31 (m, 1H), 5.25−5.18 (m, 3H), 2.98−2.77 (m, 2H), 2.62−2.37 (m, 2H), 0.87 (s, 9H), 0.17 (s, 3H), 0.15 (s, 3H). 13C NMR (75 MHz, CDCl3): δ 152.2, 145.8, 138.0, 135.2, 134.0, 130.7, 130.0, 129.1, 127.3, 126.4, 126.2, 124.8, 124.7, 122.9, 118.0, 116.0, 45.4, 29.8, 29.5, 26.0, 18.5, −2.9, −3.0. IR (film): νmax (cm−1) 3065, 3017, 2954, 2931, 2888, 2857, 1626, 1592, 1566, 1469, 1419, 1362, 1335, 1256, 1193, 1073, 1002, 968, 897, 809, 779, 759, 724, 677. ESI-MS (m/z): exact mass calcd for C25H32BrOSi [M + H]+, 455.1400; found, 455.1396. Compound (S)-3aj: colorless oil, 209.2 mg, 94% yield, 95% ee. b/l > 20/1 [Phenomenex lux 5 μ Cellulose-1 (0.46 cm × 25 cm); methol/water = 90/10; flow rate 0.7 mL/min; detection wavelength 254 nm; tR = 17.60 (major), 15.86 (minor) min]. [α]D20 = −73.5 (c = 2.0, CHCl3). 1H NMR (300 MHz, CDCl3): δ 7.60 (s, 1H), 7.50−7.31 (m, 3H), 7.10−7.07 (m, 1H), 6.96−6.92 (m, 2H), 6.81−6.78 (m, 1H), 6.47−6.34 (m, 1H), 5.28−5.21 (m, 3H), 2.96−2.81 (m, 2H), 2.63−2.41 (m, 2H), 0.85 (s, 9H), 0.16 (s, 3H), 0.14 (s, 3H). 13C NMR (75 MHz, CDCl3): δ 152.3, 144.3, 137.8, 135.3, 134.0, 131.1, 131.1, 130.7 (q, J = 31.7 Hz), 128.8, 127.3, 126.2, 124.6 (q, J = 6.9 Hz), 124.6 (q, J = 275.7 Hz), 124.4 (q, J = 4.1 Hz), 122.9 (q, J = 3.5 Hz), 118.1, 115.8, 45.5, 29.7, 29.5, 25.9, 18.4, −3.1, −3.1. 19F NMR (282 MHz): δ −62.7. IR (film): νmax (cm−1) 3066, 2950, 2933, 2884, 2859, 2831, 1626, 1568, 1487, 1438, 1361, 1326, 1260, 1194, 1161, 1120, 1076, 1028, 1000, 967, 927, 901, 822, 775, 754, 723, 697, 674. ESI-MS (m/z): exact mass calcd for C26H32F3OSi [M + H]+, 445.2169; found, 445.2164. Compound (S)-3ak: colorless oil, 143.9 mg, 75% yield, 93% ee. b/l > 20/1 [Daicel Chiralcel OD-H (0.46 cm × 25 cm); CO2/2-propanol = 95/5; flow rate 1.3 mL/min; detection wavelength 230 nm; tR = 9.74 (major), 10.28 (minor) min]. [α]D20 = −22.2 (c = 2.0, CHCl3). 1 H NMR (400 MHz, CDCl3): δ 7.11−7.06 (m, 2H), 7.01−6.89 (m, 4H), 6.82−6.81 (m, 1H), 6.50−6.41 (m, 1H), 5.44 (d, J = 7.2 Hz, 1H), 5.24 (d, J = 16.8 Hz, 1H), 5.19(d, J = 10.0 Hz, 1H), 2.94−2.80 (m, 2H), 2.57−2.39 (m, 2H), 0.92 (s, 9H), 0.19 (s, 3H), 0.18 (s, 3H). 13 C NMR (100 MHz, CDCl3): δ 151.6, 148.1, 138.1, 134.8, 133.7, 126.9, 126.6, 125.7, 124.8, 124.3, 123.7, 123.4, 116.7, 116.4, 41.5, 29.5, 29.2, 25.7, 18.2, −3.4. IR (film): νmax (cm−1) 3071, 2954, 2931, 2888, 2857, 1626, 1568, 1486, 1467, 1363, 1335, 1256, 1194, 1160, 1003, 968, 917, 882, 830, 780, 758, 692. ESI-MS (m/z): exact mass calcd for C23H31OSSi [M + H]+, 383.1859; found, 383.1859. Compound (S)-3al: colorless oil, 91.0 mg, 58% yield, 88% ee. b/l > 20/1 [Daicel Chiralcel OJ-RH (0.46 cm × 15 cm); 20 mM HCOONH4 (aq) /MeOH = 20/80; flow rate 0.9 mL/min; detection wavelength 220 nm; tR = 23.66 (major), 31.65 (minor) min]. [α]D20 = 44.1 (c = 2.0, CHCl3). 1H NMR (400 MHz, CDCl3): δ 7.31 (d, J = 5.7 Hz, 1H), 7.10−7.06 (m, 2H), 6.97 (t, J = 5.7 Hz, 1H), 6.14−6.06 (m, 1H), 5.08 (d, J = 18.0 Hz, 1H), 5.08 (d, J = 10.8 Hz, 1H), 4.10− 4.04 (m, 1H), 2.47−2.38 (m, 1H), 2.36−2.27 (m, 1H), 1.35 (d, J = 7.2 Hz, 3H), 0.97 (s, 9H), 0.20 (s, 3H), 0.19 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 150.0, 143.4, 135.7, 134.0, 126.9, 125.7, 124.3, 124.1, 118.4, 112.7, 33.2, 29.5, 29.4, 25.8, 18.2, 17.1, −3.4, −3.5. IR (film): νmax (cm−1) 3077, 2957, 2932, 2888, 2858, 1627, 1568, 1486, 1362, 1335, 1256, 1192, 1158, 1084, 1041, 1001, 952, 907, 838, 810, 780, 728, 677. ESI-MS (m/z): exact mass calcd for C20H31OSi [M + H]+, 315.2139; found, 315.2146. Compound (S)-3ba: colorless oil, 166.9 mg, 85% yield, 96% ee. b/l > 20/1 [Phenomenex lux 5 μ Cellulose-3 (0.46 cm × 25 cm); acetonitrile/water = 60/40; flow rate 0.7 mL/min; detection D

DOI: 10.1021/acs.organomet.9b00416 Organometallics XXXX, XXX, XXX−XXX

Article

Organometallics wavelength 254 nm; tR = 27.42 (major), 24.94 (minor) min]. [α]D20 = −85.2 (c = 1.0, CHCl3). 1H NMR (400 MHz, CDCl3): δ 7.31−7.24 (m, 5H), 7.18−7.13 (m, 1H), 6.79−6.74 (m, 2H), 6.60−6.55 (m, 1H), 6.42−6.34 (m, 1H), 5.32 (d, J = 7.6 Hz, 1H), 5.24−5.17 (m, 2H), 2.94−2.78 (m, 2H), 2.59−2.39 (m, 2H), 0.89 (s, 9H), 0.18 (s, 3H), 0.14 (s, 3H). 13C NMR (75 MHz, CDCl3): δ 160.2 (d, J = 241.9 Hz), 151.0, 142.8, 138.5, 136.4 (d, J = 6.8 Hz), 131.2, 128.5, 127.7, 126.4 (d, J = 7.4 Hz), 126.0, 117.4, 116.1, 114.3 (d, J = 21.1 Hz), 112.3 (d, J = 20.6 Hz), 45.1, 29.6, 29.5, 26.0, 18.4, −3.0, −3.1. 19F NMR (376 MHz): δ −119.3. IR (film): νmax (cm−1) 3080, 3061, 3027, 2954, 2932, 2889, 2858, 1629, 1606, 1584, 1494, 1468, 1358, 1329, 1253, 1195, 1146, 1110, 1006, 974, 918, 887, 838, 780, 728, 699, 669. ESI-MS (m/z): exact mass calcd for C25H32FOSi [M + H]+, 395.2201; found, 395.2212. Compound (S)-3ca: colorless oil, 182.2 mg, 88% yield, 94% ee. b/l > 20/1 [Phenomenex lux 5 μ Cellulose-3 (0.46 cm × 25 cm); acetonitrile/water = 85/15; flow rate 0.7 mL/min; detection wavelength 254 nm; tR = 6.90 (major), 6.34 (minor) min]. [α]D20 = −66.5 (c = 1.0, CHCl3). 1H NMR (400 MHz, CDCl3): δ 7.29−7.23 (m, 5H), 7.18−7.13 (m, 1H), 7.03 (d, J = 2.4 Hz, 1H), 6.84 (dd, J = 8.4, 2.4 Hz, 1H), 6.73 (d, J = 8.4 Hz, 1H), 6.41−6.33 (m, 1H), 5.31 (d, J = 7.6 Hz, 1H), 5.22 (d, J = 10.0 Hz, 1H), 5.18 (d, J = 16.8 Hz, 1H), 2.93−2.78 (m, 2H), 2.58−2.40 (m, 2H), 0.89 (s, 9H), 0.18 (s, 3H), 0.14 (s, 3H). 13C NMR (75 MHz, CDCl3): δ 152.0, 142.7, 138.3, 136.0, 133.9, 129.6, 128.5, 127.7 127.1, 126.4, 126.0, 125.9, 117.5, 116.1, 45.0, 29.5, 29.3, 26.0, 18.4, −3.1. IR (film): νmax (cm−1) 3060, 3025, 2954, 2931, 2888, 2856, 1620, 1597, 1487, 1469, 1358, 1330, 1247, 1200, 1124, 1097, 1030, 1003, 973, 919, 895, 838, 816, 775, 743, 694, 655. ESI-MS (m/z): exact mass calcd for C25H32ClOSi [M + H]+, 411.1905; found, 411.1922. Compound (S)-3da: colorless oil, 182.8 mg, 81% yield, 97% ee. b/l > 20/1 [Phenomenex lux 5 μ Cellulose-3 (0.46 cm × 25 cm); acetonitrile/water = 85/15; flow rate 0.7 mL/min; detection wavelength 254 nm; tR = 7.48 (major), 6.67 (minor) min]. [α]D20 = −60.0 (c = 2.0, CHCl3). 1H NMR (400 MHz, CDCl3): δ 7.29−7.23 (m, 5H), 7.19−7.14 (m, 2H), 6.99 (dd, J = 8.4, 2.4 Hz, 1H), 6.68 (d, J = 8.4 Hz, 1H), 6.41−6.32 (m, 1H), 5.31 (d, J = 7.6 Hz, 1H), 5.22 (d, J = 10.0 Hz, 1H), 5.18 (d, J = 17.2 Hz, 1H), 2.93−2.78 (m, 2H), 2.57−2.39 (m, 2H), 0.87 (s, 9H), 0.18 (s, 3H), 0.14 (s, 3H). 13C NMR (75 MHz, CDCl3): δ 152.2, 142.6, 138.2, 136.3, 134.4, 129.9, 128.8, 128.5, 127.6, 126.7, 126.0, 117.7, 117.5, 116.2, 44.9, 29.5, 29.2, 25.9, 18.4, −3.1. IR (film): v max (cm−1) = 3062, 2954, 2932, 2889, 2858, 1620, 1598, 1486, 1470, 1358, 1328, 1257, 1201, 1123, 1085, 1032, 1003, 972, 918, 892, 838, 806, 775, 745, 723, 695, 677, 646. ESI-MS (m/z): exact mass calcd for C25H32BrOSi [M + H]+, 455.1400; found, 455.1406. Compound (S)-3ea: colorless oil, 177.6 mg, 88% yield, 96% ee. b/l > 20/1 [Phenomenex lux 5 μ Cellulose-1 (0.46 cm × 25 cm); acetonitrile/water = 90/10; flow rate 0.7 mL/min; detection wavelength 214 nm; tR = 7.48 (major), 6.67 (minor) min]. [α]D20 = −81.1 (c = 0.5, CHCl3). 1H NMR (400 MHz, CDCl3): δ 7.31−7.29 (m, 2H), 7.26−7.22 (m, 2H), 7.16−7.11 (m, 1H), 6.86 (t, J = 8.4 Hz, 1H), 6.57 (d, J = 8.0 Hz, 1H), 6.51 (d, J = 8.0 Hz, 1H), 6.46−6.36 (m, 1H), 5.30 (d, J = 7.6 Hz, 1H), 5.25−5.22 (m, 1H), 5.21−5.20 (m, 1H), 3.78 (s, 3H), 3.04−2.96 (m, 1H), 2.86−2.76 (m, 1H), 2.56− 2.36 (m, 2H), 0.88 (s, 9H), 0.17 (s, 3H), 0.13 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 155.7, 151.8, 143.0, 138.7, 136.6, 128.1, 127.4, 125.9, 125.5, 121.5, 118.3, 116.9, 116.2, 107.2, 55.4, 45.1, 29.0, 25.7, 21.0, 18.2, −3.3, −3.4. IR (film): νmax (cm−1) 2951, 2929, 2887, 2856, 1627, 1596, 1468, 1360, 1256, 1212, 1194, 1033, 1002, 914, 852, 836, 811, 780, 737, 718, 697, 681. ESI-MS (m/z): exact mass calcd for C26H35O2Si [M + H]+, 407.2401; found, 407.2403. Procedure for Aromatization of Allylic-Substituted Tetralone. To a diastereoisomeric mixture of 3a (1.35 g, 5.15 mmol) in methanol (20 mL) was added 10% Pd/C (0.30 g). Then the reaction flask was charged with 1 atm of hydrogen. The reaction mixture was stirred at room temperature until the starting material disappeared (monitored by TLC). The crude reaction mixture was filtered with Celite and washed with EtOAc (20 mL, three times). The solvents were removed under reduced pressure. Then the residue was purified

by silica gel column chromatography (PE/EtOAc = 20/1 to 10/1) to afford 4a (1.31 g, 95% yield). In a dried flask were placed 4a (131.0 mg, 0.5 mmol) and CH3CN (20 mL), and then NBS (89.0 mg, 0.5 mmol, 1 equiv) and TBSOTf (27 mg, 0.2 equiv) were added in the dark. The reaction mixture was stirred at room temperature. After the reaction was complete (monitored by TLC), it was quenched by brine (0.5 mL). The organic solvents were removed under reduced pressure. After the mixture was extracted with EtOAc (10 mL, three times), the combined organic layers were dried over anhydrous Na2SO4 and then filtered. The solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography (PE/EtOAc = 100/1 to 50/1) to afford 5a. Compound (S)-5a: colorless oil, 118.0 mg, 90% yield, 93% ee [Daicel Chiralpak AD-H (0.46 cm × 25 cm); n-hexane/2-propanol = 97/3; flow rate 0.6 mL/min; detection wavelength 230 nm; tR = 21.66 (major), 24.57 (minor) min]. [α]D20 = −154.3 (c = 3.0, CHCl3). 1H NMR (400 MHz, CDCl3): δ 8.07 (d, J = 8.7 Hz, 1H), 7.77 (d, J = 8.1 Hz, 1H), 7.65 (d, J = 9.0 Hz, 1H), 7.39 (dt, J = 1.2, 6.6 Hz, 1H), 7.46−7.17 (m, 7H), 6.98 (d, J = 8.7 Hz, 1H), 4.93−4.99 (m, 1H), 2.39−2.53 (m, 1H), 2.20−2.35 (m, 1H), 0.90 (t, J = 7.5 Hz, 3H). 13C NMR (75 MHz, CDCl3): δ 152.0, 143.7, 134.1, 129.9, 129.1, 129.1, 129.0, 127.8, 126.8, 126.7, 123.5, 123.3, 122.7, 119.4, 42.4, 24.6, 13.0. IR (film): νmax (cm−1) 3536, 3507, 3482, 3454, 3057, 3026, 2964, 2933, 2872, 1948, 1703, 1622, 1600, 1513, 1452, 1390, 1249, 1201, 1147, 1028, 947, 862, 807, 747, 701, 620; EI-MS (m/z): exact mass calcd for C19H18O [M]+, 262.1358; found, 262.1356.

■

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.organomet.9b00416. Experimental procedures and analysis data for all new compounds (PDF)

■

AUTHOR INFORMATION

Corresponding Authors

*E-mail for Q.G.: [email protected]. *E-mail for S.-L.Y.: [email protected]. ORCID

Qing Gu: 0000-0003-4963-2271 Shu-Li You: 0000-0003-4586-8359 Author Contributions †

D.-S.Z. and Z.-L.Z. contributed equally to this work.

Notes

The authors declare no competing financial interest.

■

ACKNOWLEDGMENTS We thank the National Key R&D Program of China (2016YFA0202900), the National Natural Science Foundation of China (21821002, 21572252), and the CAS (XDB20000000, QYZDY-SSW-SLH012) for generous financial support.

■

REFERENCES

(1) For recent reviews on Ir-catalyzed allylic substitution reactions, see: (a) Helmchen, G.; Pfaltz, A. Phosphinooxazolines-A New Class of Versatile, Modular P,N-Ligands for Asymmetric Catalysis. Acc. Chem. Res. 2000, 33, 336. (b) Miyabe, H.; Takemoto, Y. Regio- and Stereocontrolled Palladium- or Iridium-Catalyzed Allylation. Synlett 2005, 1641. (c) Takeuchi, R.; Kezuka, S. Iridium-Catalyzed Formation of Carbon−Carbon and Carbon−Heteroatom Bonds. Synthesis 2006, 2006, 3349. (d) Helmchen, G.; Dahnz, A.; Dübon, P.; Schelwies, M.; Weihofen, R. Iridium-catalysed Asymmetric Allylic

E

DOI: 10.1021/acs.organomet.9b00416 Organometallics XXXX, XXX, XXX−XXX

Article

Organometallics Substitutions. Chem. Commun. 2007, 675. (e) Hartwig, J. F.; Stanley, L. M. Mechanistically Driven Development of Iridium Catalysts for Asymmetric Allylic Substitution. Acc. Chem. Res. 2010, 43, 1461. (f) Hartwig, J. F.; Pouy, M. J. Iridium-Catalyzed Allylic Substitution. Top. Organomet. Chem. 2011, 34, 169. (g) Liu, W.-B.; Xia, J.-B.; You, S.-L. Iridium-Catalyzed Asymmetric Allylic Substitutions. Top. Organomet. Chem. 2011, 38, 155. (h) Tosatti, P.; Nelson, A.; Marsden, S. P. Recent Advances and Applications of IridiumCatalysed Asymmetric Allylic Substitution. Org. Biomol. Chem. 2012, 10, 3147. (i) Hethcox, J. C.; Shockley, S. E.; Stoltz, B. M. Iridium-Catalyzed Diastereo-, Enantio-, and Regioselective Allylic Alkylation with Prochiral Enolates. ACS Catal. 2016, 6, 6207. (j) Qu, J.; Helmchen, G. Applications of Iridium-Catalyzed Asymmetric Allylic Substitution Reactions in Target-Oriented Synthesis. Acc. Chem. Res. 2017, 50, 2539. (k) Deng, Y.; Yang, W.; Yang, X.; Yang, D. Progress in Iridium-Catalyzed Asymmetric Allylic Substitution Reactions with Allylic Esters. Chin. J. Org. Chem. 2017, 37, 3039. (l) Cheng, Q.; Tu, H.-F.; Zheng, C.; Qu, J.-P.; Helmchen, G.; You, S.L. Iridium-Catalyzed Asymmetric Allylic Substitution Reactions. Chem. Rev. 2019, 119, 1855. (2) For recent examples of iridium-catalyzed asymmetric allylic substitution reactions, see: (a) Liu, J.; Cao, C.-G.; Sun, H.-B.; Zhang, X.; Niu, D. Catalytic Asymmetric Umpolung Allylation of Imines. J. Am. Chem. Soc. 2016, 138, 13103. (b) Liu, W.-B.; Okamoto, N.; Alexy, E. J.; Hong, A. Y.; Tran, K.; Stoltz, B. M. Enantioselective γAlkylation of α,β-Unsaturated Malonates and Ketoesters by a Sequential Ir-Catalyzed Asymmetric Allylic Alkylation/Cope Rearrangement. J. Am. Chem. Soc. 2016, 138, 5234. (c) Hethcox, J. C.; Shockley, S. E.; Stoltz, B. M. Iridium-Catalyzed Stereoselective Allylic Alkylation Reactions with Crotyl Chloride. Angew. Chem., Int. Ed. 2016, 55, 16092. (d) Jiang, X.; Beiger, J. J.; Hartwig, J. F. Stereodivergent Allylic Substitutions with Aryl Acetic Acid Esters by Synergistic Iridium and Lewis Base Catalysis. J. Am. Chem. Soc. 2017, 139, 87. (e) Liu, X.-J.; You, S.-L. Enantioselective Iridium-Catalyzed Allylic Substitution with 2-Methylpyridines. Angew. Chem., Int. Ed. 2017, 56, 4002. (f) Wang, Y.; Zheng, C.; You, S.-L. Ir-Catalyzed Asymmetric Allylic Dearomatization by a Desymmetrization Strategy. Angew. Chem., Int. Ed. 2017, 56, 15093. (g) Shockley, S. E.; Hethcox, J. C.; Stoltz, B. M. Enantioselective Synthesis of Acyclic α-Quaternary Carboxylic Acid Derivatives through Iridium-Catalyzed Allylic Alkylation. Angew. Chem., Int. Ed. 2017, 56, 11545. (h) Butcher, T. W.; Hartwig, J. F. Enantioselective Synthesis of Tertiary Allylic Fluorides by Iridium-Catalyzed Allylic Fluoroalkylation. Angew. Chem., Int. Ed. 2018, 57, 13125. (i) Hethcox, J. C.; Shockley, S. E.; Stoltz, B. M. Enantioselective Synthesis of Vicinal All-Carbon Quaternary Centers via Iridium-Catalyzed Allylic Alkylation. Angew. Chem., Int. Ed. 2018, 57, 8664. (j) Yang, Z.-P.; Jiang, R.; Zheng, C.; You, S.-L. Iridium-Catalyzed Intramolecular Asymmetric Allylic Alkylation of Hydroxyquinolines: Simultaneous Weakening of the Aromaticity of Two Consecutive Aromatic Rings. J. Am. Chem. Soc. 2018, 140, 3114. (k) Huang, L.; Cai, Y.; Zhang, H.-J.; Zheng, C.; Dai, L.-X.; You, S.-L. Highly Diastereo- and Enantioselective Synthesis of Quinuclidine Derivatives by an Iridium-Catalyzed Intramolecular Allylic Dearomatization Reaction. CCS Chem. 2019, 1, 106. (l) Yang, Z.-P.; Jiang, R.; Wu, Q.-F.; Huang, L.; Zheng, C.; You, S.-L. IridiumCatalyzed Intramolecular Asymmetric Allylic Dearomatization Reaction of Benzene Derivatives. Angew. Chem., Int. Ed. 2018, 57, 16190. (m) He, Z.-T.; Hartwig, J. F. Enantioselective α-Functionalizations of Ketones via Allylic Substitution of Silyl Enol Ethers. Nat. Chem. 2019, 11, 177. (n) Wang, Y.; Zhang, W.-Y.; You, S.-L. Ketones and Aldehydes as O-Nucleophiles in Iridium-Catalyzed Intramolecular Asymmetric Allylic Substitution Reaction. J. Am. Chem. Soc. 2019, 141, 2228. (o) Chen, J.; Liang, Q.; Zhao, X. Chemoselective, Regioselective, and Enantioselective Allylations of NH2OH under Iridium Catalysis. Org. Lett. 2019, 21, 5383. (3) For recent examples of iridium-catalyzed diastereodivergent allylic substitution reactions, see ref 2d and (a) Krautwald, S.; Sarlah, D.; Schafroth, M. A.; Carreira, E. M. Enantio- and Diastereodivergent Dual Catalysis: α-Allylation of Branched Aldehydes. Science 2013,

340, 1065. (b) Krautwald, S.; Schafroth, M. A.; Sarlah, D.; Carreira, E. M. Stereodivergent α-Allylation of Linear Aldehydes with Dual Iridium and Amine Catalysis. J. Am. Chem. Soc. 2014, 136, 3020. (c) Sandmeier, T.; Krautwald, S.; Zipfel, H. F.; Carreira, E. M. Stereodivergent Dual Catalytic α-Allylation of Protected α-Aminoand α-Hydroxyacetaldehydes. Angew. Chem., Int. Ed. 2015, 54, 14363. (d) Nœsborg, L.; Halskov, K. S.; Tur, F.; Mønsted, S. M. N.; Jørgensen, K. A. Asymmetric γ-Allylation of α, β-Unsaturated Aldehydes by Combined Organocatalysis and Transition-Metal Catalysis. Angew. Chem., Int. Ed. 2015, 54, 10193. (e) Huo, X.; He, R.; Zhang, X.; Zhang, W. An Ir/Zn Dual Catalysis for Enantio- and Diastereodivergent α-Allylation of α-Hydroxyketones. J. Am. Chem. Soc. 2016, 138, 11093. (f) Huo, X.; Zhang, J.; Fu, J.; He, R.; Zhang, W. Ir/Cu Dual Catalysis: Enantio- and Diastereodivergent Access to α,α-Disubstituted α-Amino Acids Bearing Vicinal Stereocenters. J. Am. Chem. Soc. 2018, 140, 2080. (g) Jiang, X.; Boehm, P.; Hartwig, J. F. Stereodivergent Allylation of Azaaryl Acetamides and Acetates by Synergistic Iridium and Copper Catalysis. J. Am. Chem. Soc. 2018, 140, 1239. (h) Wei, L.; Zhu, Q.; Xu, S.-M.; Chang, X.; Wang, C.-J. Stereodivergent Synthesis of α,α-Disubstituted α-Amino Acids via Synergistic Cu/Ir Catalysis. J. Am. Chem. Soc. 2018, 140, 1508. (4) For selected examples of allylic alkylation reactions, see: (a) Bandini, M.; Melloni, A.; Umani-Ronchi, A. New Versatile PdCatalyzed Alkylation of Indoles via Nucleophilic Allylic Substitution: Controlling the Regioselectivity. Org. Lett. 2004, 6, 3199. (b) Kimura, M.; Futamata, M.; Mukai, R.; Tamaru, Y. Pd-Catalyzed C3-Selective Allylation of Indoles with Allyl Alcohols Promoted by Triethylborane. J. Am. Chem. Soc. 2005, 127, 4592. (c) Bandini, M.; Melloni, A.; Piccinelli, F.; Sinisi, R.; Tommasi, S.; Umani-Ronchi, A. Highly Enantioselective Synthesis of Tetrahydro-β-Carbolines and Tetrahydro-γ-Carbolines via Pd-Catalyzed Intramolecular Allylic Alkylation. J. Am. Chem. Soc. 2006, 128, 1424. (d) Cheung, H. Y.; Yu, W.-Y.; Lam, F. L.; Au-Yeung, T. T.-L.; Zhou, Z.; Chan, T. H.; Chan, A. S. C. Enantioselective Pd-Catalyzed Allylic Alkylation of Indoles by a New Class of Chiral Ferrocenyl P/S Ligands. Org. Lett. 2007, 9, 4295. (e) Liu, W.-B.; He, H.; Dai, L.-X.; You, S.-L. Ir-Catalyzed Regio- and Enantioselective Friedel−Crafts-Type Allylic Alkylation of Indoles. Org. Lett. 2008, 10, 1815. (f) Sundararaju, B.; Achard, M.; Demerseman, B.; Toupet, L.; Sharma, G. V. M.; Bruneau, C. Ruthenium(IV) Complexes Featuring P, O-Chelating Ligands: Regioselective Substitution Directly from Allylic Alcohols. Angew. Chem., Int. Ed. 2010, 49, 2782. (g) Cao, Z.; Liu, Y.; Liu, Z.; Feng, X.; Zhuang, M.; Du, H. Pd-Catalyzed Asymmetric Allylic Alkylation of Indoles and Pyrroles by Chiral Alkene-Phosphine Ligands. Org. Lett. 2011, 13, 2164. (h) Hoshi, T.; Sasaki, K.; Sato, S.; Ishii, Y.; Suzuki, T.; Hagiwara, H. Highly Enantioselective Pd-Catalyzed Allylic Alkylation of Indoles Using Sulfur-MOP Ligand. Org. Lett. 2011, 13, 932. (i) Xu, Q.-L.; Zhuo, C.-X.; Dai, L.-X.; You, S.-L. Highly Enantioselective Synthesis of Tetrahydrocarbolines via Iridium-Catalyzed Intramolecular Friedel-Crafts Type Allylic Alkylation Reactions. Org. Lett. 2013, 15, 5909. (j) Xu, Q.-L.; Dai, L.-X.; You, S.-L. Diversity Oriented Synthesis of Indole-based Periannulated Compounds via AllylicAlkylation Reactions. Chem. Sci. 2013, 4, 97. (5) For selected examples of intramolecular allylic alkylation of phenols, see: (a) Nemoto, T.; Ishige, Y.; Yoshida, M.; Kohno, Y.; Kanematsu, M.; Hamada, Y. Novel Method for Synthesizing Spiro[4.5]cyclohexadienones through a Pd-Catalyzed Intramolecular ipso-Friedel-Crafts Allylic Alkylation of Phenols. Org. Lett. 2010, 12, 5020. (b) Wu, Q.-F.; Liu, W.-B.; Zhuo, C.-X.; Rong, Z.-Q.; Ye, K.-Y.; You, S.-L. Iridium-Catalyzed Intramolecular Asymmetric Allylic Dearomatization of Phenols. Angew. Chem., Int. Ed. 2011, 50, 4455. (c) Xu, Q.-L.; Dai, L.-X.; You, S.-L. Enantioselective Synthesis of Tetrahydroisoquinolines via Iridium-Catalyzed Intramolecular Friedel-Crafts-Type Allylic Alkylation of Phenols. Org. Lett. 2012, 14, 2579. (d) Yoshida, M.; Nemoto, T.; Zhao, Z.; Ishige, Y.; Hamada, Y. Enantioselective Construction of All-carbon Quaternary Spirocenters through a Pd-catalyzed Asymmetric Intramolecular ipso-Friedel− Crafts Allylic Alkylation of Phenols. Tetrahedron: Asymmetry 2012, 23, 859. (e) Suzuki, Y.; Nemoto, T.; Kakugawa, K.; Hamajima, A.; F

DOI: 10.1021/acs.organomet.9b00416 Organometallics XXXX, XXX, XXX−XXX

Article

Organometallics

Phenols and 2-Hydroxypyridines. Chem. - Eur. J. 2016, 22, 14655. (f) Discolo, C. A.; Graves, A. G.; Deardorff, D. R. Regio- and Stereospecific C- and O-Allylation of Phenols via π-Allyl Pd Complexes Derived from Allylic Ester Carbonates. J. Org. Chem. 2017, 82, 1034. (g) Zhao, Z.-L.; Gu, Q.; Wu, X.-Y.; You, S.-L. Anilines as C-Nucleophiles in Ir-Catalyzed Intramolecular Asymmetric Allylic Substitution Reactions. Chem. - Asian J. 2017, 12, 2680. (h) Tian, H.; Zhang, P.; Peng, F.; Yang, H.; Fu, H. Chiral Cyclic Ligand-Enabled Iridium-Catalyzed Asymmetric Arylation of Unactivated Racemic Allylic Alcohols with Anilines. Org. Lett. 2017, 19, 3775. (8) (a) Guha, S. K.; Wu, B.; Kim, B. S.; Baik, W.; Koo, S. TMS·OTfCatalyzed α-Bromination of Carbonyl Compounds by N-Bromosuccinimide. Tetrahedron Lett. 2006, 47, 291. (b) Yi, C. S.; Lee, D. W. Efficient Dehydrogenation of Amines and Carbonyl Compounds Catalyzed by a Tetranuclear Ruthenium-μ-oxo-μ-hydroxo-hydride Complex. Organometallics 2009, 28, 947. (c) Liang, Y.-F.; Song, S.; Ai, L.; Li, X.; Jiao, N. Highly Efficient Metal-free Approach to Meta- and Multiple-substituted Phenols via A Simple Oxidation of Cyclohexenones. Green Chem. 2016, 18, 6462. (d) Kelly, P. P.; Lipscomb, D.; Quinn, D. J.; Lemon, K.; Caswell, J.; Spratt, J.; Kosjek, B.; Truppo, M.; Moody, T. S. Ene Reductase Enzymes for the Aromatisation of Tetralones and Cyclohexenones to Naphthols and Phenols. Adv. Synth. Catal. 2016, 358, 731. (9) (a) de Vries, A. H. M.; Meetsma, A.; Feringa, B. L. Enantioselective Conjugate Addition of Dialkylzinc Reagents to Cyclic and Acyclic Enones Catalyzed by Chiral Copper Complexes of New Phosphorus Amidites. Angew. Chem., Int. Ed. Engl. 1996, 35, 2374. (b) Teichert, J. F.; Feringa, B. L. Phosphoramidites: Privileged Ligands in Asymmetric Catalysis. Angew. Chem., Int. Ed. 2010, 49, 2486. (c) Feringa, B. L.; Pineschi, M.; Arnold, L. A.; Imbos, R.; de Vries, A. H. M. Highly Enantioselective Catalytic Conjugate Addition and Tandem Conjugate Addition−Aldol Reactions of Organozinc Reagents. Angew. Chem., Int. Ed. Engl. 1997, 36, 2620. (10) Alexakis, A.; Polet, D. Very Efficient Phosphoramidite Ligand for Asymmetric Iridium-Catalyzed Allylic Alkylation. Org. Lett. 2004, 6, 3529. (11) (a) Liu, W.-B.; He, H.; Dai, L.-X.; You, S.-L. Synthesis of 2Methylindoline- and 2-Methyl-1,2,3,4-tetrahydroquinoline-Derived Phosphoramidites and Their Applications in Iridium-Catalyzed Allylic Alkylation of Indoles. Synthesis 2009, 2009, 2076. (b) Liu, W.-B.; Zheng, C.; Zhuo, C.-X.; Dai, L.-X.; You, S.-L. Iridium-Catalyzed Allylic Alkylation Reaction with N-Aryl Phosphoramidite Ligands: Scope and Mechanistic Studies. J. Am. Chem. Soc. 2012, 134, 4812. (c) Zhang, X.; You, S.-L. THQphos in Ir-Catalyzed Asymmetric Allylic Substitution Reactions. Chimia 2018, 72, 589. (12) Shu, C.; Leitner, A.; Hartwig, J. F. Enantioselective Allylation of Aromatic Amines after In Situ Generation of an Activated Cyclometalated Iridium Catalyst. Angew. Chem., Int. Ed. 2004, 43, 4797. (13) (a) Kiener, C. A.; Shu, C.; Incarvito, C.; Hartwig, J. F. Identification of an Activated Catalyst in the Iridium-Catalyzed Allylic Amination and Etherification. Increased Rates, Scope, and Selectivity. J. Am. Chem. Soc. 2003, 125, 14272. (b) Marković, D.; Hartwig, J. F. Resting State and Kinetic Studies on the Asymmetric Allylic Substitutions Catalyzed by Iridium-Phosphoramidite Complexes. J. Am. Chem. Soc. 2007, 129, 11680. (c) Madrahimov, S. T.; Markovic, D.; Hartwig, J. F. The Allyl Intermediate in Regioselective and Enantioselective Iridium-Catalyzed Asymmetric Allylic Substitution Reactions. J. Am. Chem. Soc. 2009, 131, 7228.

Hamada, Y. Asymmetric Synthesis of Chiral 9,10-Dihydrophenanthrenes Using Pd-Catalyzed Asymmetric Intramolecular FriedelCrafts Allylic Alkylation of Phenols. Org. Lett. 2012, 14, 2350. (f) Nemoto, T.; Zhao, Z.; Yokosaka, T.; Suzuki, Y.; Wu, R.; Hamada, Y. Palladium-Catalyzed Intramolecular ipso-Friedel−Crafts Alkylation of Phenols and Indoles: Rearomatization-Assisted Oxidative Addition. Angew. Chem., Int. Ed. 2013, 52, 2217. (g) Zhao, Z.-L.; Xu, Q.-L.; Gu, Q.; Wu, X.-Y.; You, S.-L. Enantioselective Synthesis of 4-Substituted Tetrahydroisoquinolines via Palladium-Catalyzed Intramolecular Friedel−Crafts Type Allylic Alkylation of Phenols. Org. Biomol. Chem. 2015, 13, 3086. (h) Schafroth, M. A.; Rummelt, S. M.; Sarlah, D.; Carreira, E. M. Enantioselective Iridium-Catalyzed Allylic Cyclizations. Org. Lett. 2017, 19, 3235. (6) For selected examples of O-alkylation of phenols, see: (a) Trost, B. M.; Toste, F. D. Asymmetric O- and C-Alkylation of Phenols. J. Am. Chem. Soc. 1998, 120, 815. (b) Trost, B. M.; Toste, F. D. Regioand Enantioselective Allylic Alkylation of an Unsymmetrical Substrate: A Working Model. J. Am. Chem. Soc. 1999, 121, 4545. (c) Evans, P. A.; Leahy, D. K. Regioselective and Enantiospecific Rhodium-Catalyzed Intermolecular Allylic Etherification with orthoSubstituted Phenols. J. Am. Chem. Soc. 2000, 122, 5012. (d) Evans, P. A.; Leahy, D. K. Regio- and Enantiospecific Rhodium-Catalyzed Allylic Etherification Reactions Using Copper(I) Alkoxides: Influence of the Copper Halide Salt on Selectivity. J. Am. Chem. Soc. 2002, 124, 7882. (e) Trost, B. M.; Fraisse, P. L.; Ball, Z. T. A Stereospecific Ruthenium-Catalyzed Allylic Alkylation. Angew. Chem., Int. Ed. 2002, 41, 1059. (f) Trost, B. M.; Shen, H. C.; Dong, L.; Surivet, J.-P. Unusual Effects in the Pd-Catalyzed Asymmetric Allylic Alkylations: Synthesis of Chiral Chromans. J. Am. Chem. Soc. 2003, 125, 9276. (g) López, F.; Ohmura, T.; Hartwig, J. F. Regio- and Enantioselective Iridium-Catalyzed Intermolecular Allylic Etherification of Achiral Allylic Carbonates with Phenoxides. J. Am. Chem. Soc. 2003, 125, 3426. (h) Trost, B. M.; Shen, H. C.; Dong, L.; Surivet, J.-P.; Sylvain, C. Synthesis of Chiral Chromans by the Pd-Catalyzed Asymmetric Allylic Alkylation (AAA): Scope, Mechanism, and Applications. J. Am. Chem. Soc. 2004, 126, 11966. (i) Mbaye, M. D.; Renaud, J. L.; Demerseman, B.; Bruneau, C. First Enantioselective Allylic Etherification with Phenols Catalyzed by Chiral Ruthenium Bisoxazoline Complexes. Chem. Commun. 2004, 1870. (j) Welter, C.; Dahnz, A.; Brunner, B.; Streiff, S.; Dö ubon, P.; Helmchen, G. Highly Enantioselective Syntheses of Heterocycles via Intramolecular IrCatalyzed Allylic Amination and Etherification. Org. Lett. 2005, 7, 1239. (k) Bruneau, C.; Renaud, J.-L.; Demerseman, B. Pentamethylcyclopentadienyl−Ruthenium Catalysts for Regio- and Enantioselective Allylation of Nucleophiles. Chem. - Eur. J. 2006, 12, 5178. (l) Kirsch, S. F.; Overman, L. E.; White, N. S. Catalytic Asymmetric Synthesis of Allylic Aryl Ethers. Org. Lett. 2007, 9, 911. (m) Kimura, M.; Uozumi, Y. Development of New P-Chiral Phosphorodiamidite Ligands Having a Pyrrolo[1,2-c]diazaphosphol-1-one Unit and Their Application to Regio- and Enantioselective Iridium-Catalyzed Allylic Etherification. J. Org. Chem. 2007, 72, 707. (n) Onitsuka, K.; Okuda, H.; Sasai, H. Regio- and Enantioselective O-Allylation of Phenol and Alcohol Catalyzed by a Planar-Chiral Cyclopentadienyl Ruthenium Complex. Angew. Chem., Int. Ed. 2008, 47, 1454. (7) For selected examples of intermolecular Friedel−Crafts type allylic alkylation reactions, see: (a) Tada, Y.; Satake, A.; Shimizu, I.; Yamamoto, A. Palladium-Catalyzed C-Allylation of Naphthols by Direct Use of Allylic Alcohols under Neutral Conditions. Chem. Lett. 1996, 25, 1021. (b) Kimura, M.; Fukasaka, M.; Tamaru, Y. PalladiumCatalyzed, Triethylborane-Promoted C-Allylation of Naphthols and Benzene Polyols by Direct Use of Allyl Alcohols. Synthesis 2006, 2006, 3611. (c) Fernández, I.; Hermatschweiler, R.; Breher, F.; Pregosin, P. S.; Veiros, L. F.; Calhorda, M. J. High-Yield Ruthenium-Catalyzed Friedel-Crafts-Type Allylation Reactions Using Dicationic RuIV Catalysts. Angew. Chem., Int. Ed. 2006, 45, 6386. (d) McCubbin, J. A.; Hosseini, H.; Krokhin, O. V. Boronic Acid Catalyzed FriedelCrafts Reactions of Allylic Alcohols with Electron-Rich Arenes and Heteroarenes. J. Org. Chem. 2010, 75, 959. (e) Li, C.; Breit, B. Rhodium-Catalyzed Dynamic Kinetic Asymmetric Allylation of G

DOI: 10.1021/acs.organomet.9b00416 Organometallics XXXX, XXX, XXX−XXX