Allylic Substitution of meso-1,4-Diacetoxycycloalkenes in Water with an Amphiphilic Resin-Supported Chiral Palladium Complex

Yasuhiro Uozumi; Hiroe Takenaka; Toshimasa Suzuka

doi:10.1055/s-2008-1078422

CLUSTER

Allylic Substitution of meso-1,4-Diacetoxycycloalkenes in Water with an Amphiphilic Resin-Supported Chiral Palladium Complex

Yasuhiro Uozumi*, Hiroe Takenaka, Toshimasa Suzuka
Institute for Molecular Science (IMS) and CREST, Higashiyama 5-1, Myodaiji, Okazaki 444-8787, Japan
Fax: +81(564)595574; e-Mail: uo@ims.ac.jp;

Abstract

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Abstract

Asymmetric π-allylic substitution of meso-1,4-diacetoxycyclopentene and meso-1,4-diacetoxycyclohexene with various nucleophiles was performed with an amphiphilic polystyrene-poly(ethylene glycol) (PS-PEG) resin-supported chiral imidazoindolephosphine-palladium complex in water as a single reaction medium under heterogeneous conditions to give the corresponding 1-acetoxy-4-substituted cycloalkenes with up to 99% ee.

Key words

π-allylpalladium - asymmetric catalysis - aqueous media - polymer support - palladium catalyst

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References

References and Notes

For reviews on aqueous-switching of organic transformations, see:

<A NAME="RY00308ST-1A">1a</A> Li C.-J. Chan T.-H. Organic Reactions in Aqueous Media Wiley; New York: 1997.

<A NAME="RY00308ST-1B">1b</A> Grieco PA. Organic Synthesis in Water Kluwer Academic Publishers; Dordrecht: 1997.

<A NAME="RY00308ST-1C">1c</A> Herrmann WA. Kohlpaintner CW. Angew. Chem., Int. Ed. Engl. 1993, 32: 1524

<A NAME="RY00308ST-1D">1d</A> Lindström UM. Chem. Rev. 2002, 102: 2751

For reviews on heterogeneous-switching of organic transformations, see:

<A NAME="RY00308ST-2A">2a</A> Bailey DC. Langer SH. Chem. Rev. 1981, 81: 109

<A NAME="RY00308ST-2B">2b</A> Shuttleworth SJ. Allin SM. Sharma PK. Synthesis 1997, 1217

<A NAME="RY00308ST-2C">2c</A> Shuttleworth SJ. Allin SM. Wilson RD. Nasturica D. Synthesis 2000, 1035

<A NAME="RY00308ST-2D">2d</A> Dörwald FZ. Organic Synthesis on Solid Phase Wiley-VCH; Weinheim: 2000.

<A NAME="RY00308ST-2E">2e</A> Leadbeater NE. Marco M. Chem. Rev. 2002, 102: 3217

<A NAME="RY00308ST-2F">2f</A> Ley SV. Baxendale IR. Bream RN. Jackson PS. Leach AG. Longbottom DA. Nesi M. Scott JS. Storer RI. Taylor SJ. J. Chem. Soc., Perkin Trans. 1 2000, 3815

<A NAME="RY00308ST-2G">2g</A> McNamara CA. Dixon MJ. Bradley M. Chem. Rev. 2002, 102: 3275

<A NAME="RY00308ST-2H">2h</A> Chiral Catalyst Immobilization and Recycling De Vos DE. Vankelecom IFJ. Jacobs PA. Wiley-VCH; Weinheim: 2000.

<A NAME="RY00308ST-2I">2i</A> Fan Q.-H. Li Y.-M. Chan ASC. Chem. Rev. 2002, 102: 3385

For recent reviews on solid-phase reactions using palladium catalysts, see:

<A NAME="RY00308ST-3A">3a</A> Uozumi Y. Hayashi T. Solid-Phase Palladium Catalysis for High-Throughput Organic Synthesis, In Handbook of Combinatorial Chemistry Nicolaou KC. Hanko R. Hartwig W. Wiley-VCH; Weinheim: 2002. Chap. 19.

<A NAME="RY00308ST-3B">3b</A> Uozumi Y. Top. Curr. Chem. 2004, 242: 77

For studies on polymer-supported catalysts from the author’s group, see:

<A NAME="RY00308ST-4A">4a</A> Cross-coupling: Uozumi Y. Danjo H. Hayashi T. J. Org. Chem. 1999, 64: 3384

<A NAME="RY00308ST-4B">4b</A> Carbonylation reaction: Uozumi Y. Watanabe T. J. Org. Chem. 1999, 64: 6921

<A NAME="RY00308ST-4C">4c</A> Michael addition: Shibatomi K. Nakahashi T. Uozumi Y. Synlett 2000, 1643

Suzuki-Miyaura coupling:

<A NAME="RY00308ST-4D">4d</A> Uozumi Y. Nakai Y. Org. Lett. 2002, 4: 2997

<A NAME="RY00308ST-4E">4e</A> Uozumi Y. Kikuchi M. Synlett 2005, 1775

<A NAME="RY00308ST-4F">4f</A> Heck reaction: Uozumi Y. Kimura T. Synlett 2002, 2045

<A NAME="RY00308ST-4G">4g</A> Rhodium catalysis: Uozumi Y. Nakazono M. Adv. Synth. Catal. 2002, 344: 274

(Wacker cyclization):

<A NAME="RY00308ST-4H">4h</A> Hocke H. Uozumi Y. Synlett 2002, 2049

<A NAME="RY00308ST-4I">4i</A> Hocke H. Uozumi Y. Tetrahedron 2003, 59: 619

<A NAME="RY00308ST-4J">4j</A> Sonogashira reaction: Uozumi Y. Kobayashi Y. Heterocycles 2003, 59: 71

Oxidation:

<A NAME="RY00308ST-4K">4k</A> Uozumi Y. Nakao R. Angew. Chem. Int. Ed. 2003, 42: 194

<A NAME="RY00308ST-4L">4l</A> Uozumi Y. Nakao R. Angew. Chem. 2003, 115: 204

<A NAME="RY00308ST-4M">4m</A> Yamada YMA. Arakawa T. Hocke H. Uozumi Y. Angew. Chem. Int. Ed. 2007, 46: 704

<A NAME="RY00308ST-4N">4n</A> Reduction: Nakao R. Rhee H. Uozumi Y. Org. Lett. 2005, 7: 163

<A NAME="RY00308ST-4O">4o</A> Alkylation: Yamada YMA. Uozumi Y. Org. Lett. 2006, 8: 1375

For studies on π-allylic transformations with polymer-supported complex catalysts in water, see:

<A NAME="RY00308ST-5A">5a</A> Uozumi Y. Danjo H. Hayashi T. Tetrahedron Lett. 1997, 38: 3557

<A NAME="RY00308ST-5B">5b</A> Danjo H. Tanaka D. Hayashi T. Uozumi Y. Tetrahedron 1999, 55: 14341

<A NAME="RY00308ST-5C">5c</A> Uozumi Y. Suzuka T. Kawade R. Takenaka H. Synlett 2006, 2109

For studies on heterogeneous aquacatalytic asymmetric π-allylic transformations with polymer-supported complex catalysts in water, see:

<A NAME="RY00308ST-6A">6a</A> Alkylation: Uozumi Y. Danjo H. Hayashi T. Tetrahedron Lett. 1998, 39: 8303

<A NAME="RY00308ST-6B">6b</A> Reduction with monodentate phosphine (MOP): Hocke H. Uozumi Y. Tetrahedron 2004, 60: 9297

<A NAME="RY00308ST-6C">6c</A> Alkylation: Uozumi Y. Shibatomi K. J. Am. Chem. Soc. 2001, 123: 2919

<A NAME="RY00308ST-6D">6d</A> Amination: Uozumi Y. Tanaka H. Shibatomi K. Org. Lett. 2004, 6: 281

<A NAME="RY00308ST-6E">6e</A> Cyclization: Nakai Y. Uozumi Y. Org. Lett. 2005, 7: 291

<A NAME="RY00308ST-6F">6f</A> Etherification: Uozumi Y. Kimura M. Tetrahedron: Asymmetry 2006, 17: 161

<A NAME="RY00308ST-6G">6g</A> Nitromethylation: Uozumi Y. Suzuka T. J. Org. Chem. 2006, 71: 8644

<A NAME="RY00308ST-6H">6h</A> Kobayashi Y. Tanaka D. Danjo H. Uozumi Y. Adv. Synth. Catal. 2006, 348: 1561

<A NAME="RY00308ST-6I">6i</A> Uozumi Y. Pure Appl. Chem. 2007, 79: 1481

For recent reviews on asymmetric π-allylic substitution, see:

<A NAME="RY00308ST-7A">7a</A> Acemoglu L. Williams JMJ. Handbook of Organopalladium Chemistry for Organic Synthesis Negishi E. de Meijere A. Wiley; New York: 2002.

<A NAME="RY00308ST-7B">7b</A> Trost BM. Crawley ML. Chem. Rev. 2003, 103: 2921

<A NAME="RY00308ST-8A">8a</A> Taniimori S. Tsuji Y. Kirihara M. Biosci., Biotechnol., Biochem. 2002, 66: 660

<A NAME="RY00308ST-8B">8b</A> Song ES. Yang JW. Roh EJ. Lee S.-G. Han H. Angew. Chem. Int. Ed. 2002, 41: 3852

<A NAME="RY00308ST-8C">8c</A> Trost BM. Van Vranken DL. Bingel C. J. Am. Chem. Soc. 1992, 114: 9327

<A NAME="RY00308ST-9D">9d</A> Trost B. M., Pulley S. R., Bingel C.; Tetrahedron Lett.; 1995, 36: 8737

Tenta Gel SNH₂ (purchased from Rapp Polymere) was used as the polymer support.

Chemical yield of the monosubstituted product 4 was lowered to <30% with Li₂CO₃, NaHCO₃, Na₂CO₃, or K₂CO₃.

The absolute configuration of 4 was determined by chemical correlation with (1R,4S)-cis-1-acetoxy-4-[bis(methoxy-carbonyl)methyl]-2-cyclopentene (see ref. 8a).

<A NAME="RY00308ST-13">13</A> Nishiyama H. Sakata N. Sugimoto H. Motoyama Y. Wakita H. Nagase H. Synlett 1998, 930

The absolute configuration of 6a was determined to be 1R,4S by measurement of the specific rotation (see, ref. 12). The configurations of 6b-g were tentatively assigned on the basis of the mechanistic similarity of the asymmetric induction, as depicted in Table [1] .

Palladium-Catalyzed Asymmetric Desymmetrization of meso -Cycloalkene-1,4-diacetate: Reaction conditions and results are shown in Table [1] . A typical procedure is given for the reaction with cis-1,4-diacetoxycyclopentene (meso-2) and phenol (a) in H₂O (entry 3).
To a mixture of the catalyst 1 (89 mg, 0.025 mmol) and meso-2 (92 mg, 0.5 mmol) in H₂O (2.5 mL) was added phenol (48 mg, 0.5 mmol), and the mixture was shaken at 0 °C for 18 h. The reaction mixture was filtered and the recovered resin beads were rinsed with EtOAc (3 ×). The combined filtrate was dried over anhyd Na₂SO₄. The solvent was evaporated and the residue was chromatographed on silica gel (hexane-EtOAc, 10:1) to give 1-acetoxy-4-phenoxycyclopentene (6a; 70 mg, 64% yield) and 1,4-diphenoxycyclopentene (8; 18 mg). The enantiomeric excess was determined to be 99% ee by GC analysis using a chiral stationary phase capillary column (Cyclodex CB).
Spectral and analytical data for compounds 6 are shown below, where the enantiomeric excesses were determined by GC (Cyclodex CB), unless otherwise noted: 1-Acetoxy-4-phenoxycyclopentene (6a): [α]_D ²³ +63.8 (c = 1.0, CHCl₃). ¹H NMR (CDCl₃): δ = 7.29 (t, J = 7.8 Hz, 2 H), 6.96 (t, J = 7.3 Hz, 1 H), 6.92 (d, J = 7.8 Hz, 2 H), 6.24 (d, J = 5.8 Hz, 1 H), 6.12 (d, J = 5.3 Hz, 1 H), 5.61 (br, 1 H), 5.17 (br, 1 H), 2.97 (dt, J = 7.3, 14.6 Hz, 1 H), 2.05 (s, 3 H), 1.89 (dt, J = 4.0, 14.6 Hz, 1 H). ¹³C NMR (CDCl₃): δ = 170.77, 157.77, 135.05, 134.06, 129.53, 115.34, 79.55, 76.74, 37.94, 21.08. IR (ATR): 1733, 1493, 1366, 1228, 1087, 889, 754, 692, 628 cm^-1. MS (EI): m/z (%rel intensity) = 218 (0.7) [M⁺], 43 (base peak). Anal. Calcd for C₁₃H₁₄O₃: C, 71.54; H, 6.47. Found: C, 71.49; H, 6.53. CAS registry number: 210701-09-0.
1-Acetoxy-4-(2-benzyloxyphenoxy)-2-cyclopentene (6b): [α]_D ²⁸ -20.5 (c = 1.0, CHCl₃); 97% ee. ¹H NMR (CDCl₃): δ = 7.43-7.27 (m, 4 H), 6.89-6.98 (m, 5 H), 6.26 (br d, J = 4.8 Hz, 1 H), 6.09 (br d, J = 4.8 Hz, 1 H), 5.57 (br, 1 H), 5.17 (br, 1 H), 5.12 (s, 2 H), 2.93 (dt, J = 7.3, 14.6 Hz, 1 H), 2.04 (s, 3 H), 1.98 (dt, J = 4.3, 14.6 Hz, 1 H). ¹³C NMR (CDCl₃): δ = 170.88, 149.49, 148.28, 137.32, 134.67, 133.73, 128.45, 127.78, 127.29, 122.21, 121.70, 117.09, 115.60, 81.72, 76.79, 71.31, 38.08, 21.13. IR (ATR): 1732, 1499, 1452, 1366, 1236, 1212, 1083, 1012, 896, 742, 697, 627 cm^-1. MS (EI): m/z (%rel intensity) = 324 (1) [M⁺], 91 (base peak). Anal Calcd for C₂₀H₂₀O₄: C, 74.06; H, 6.21. Found: C, 73.94; H, 6.28.
1-Acetoxy-4-(2-chlorophenoxy)-2-cyclopentene (6c): [α]_D ²⁶ -58.0 (c = 1.0, CHCl₃). ¹H NMR (CDCl₃): δ = 7.37 (dd, J = 1.8, 7.9 Hz, 1 H), 7.20 (dt, J = 1.8, 7.9 Hz, 1 H), 6.95 (d, J = 7.9 Hz, 1 H), 6.92 (t, J = 7.9 Hz, 1 H), 6.26 (d, J = 5.5 Hz, 1 H), 6.14 (J = 5.5 Hz, 1 H), 5.60 (br, 1 H), 5.17 (br, 1 H), 2.99 (dt, J = 7.3, 14.6 Hz, 1 H), 2.06 (s, 3 H), 1.96 (dt, J = 4.3, 14.6 Hz, 1 H). ¹³C NMR (CDCl₃): δ = 170.84, 153.65, 134.65, 134.46, 130.57, 127.66, 123.71, 121.94, 115.26, 81.33, 76.61, 38.02, 21.11. IR (ATR): 1237, 1090, 902, 730, 649, 630 cm^-1. MS (EI): m/z (%rel intensity): = 252 (0.02) [M⁺], 43 (base peak).
1-Acetoxy-4-(2-bromophenoxy)-2-cyclopentene (6d): [α]_D ²⁵ -100.8 (c = 1.1, CHCl₃); 95% ee. ¹H NMR (CDCl₃): δ = 7.55 (dd, J = 1.2, 7.9 Hz, 1 H), 7.25 (td, J = 1.2, 7.3 Hz, 1 H), 6.94 (d, J = 1.2 Hz, 1 H), 6.85 (td, J = 1.2, 7.9 Hz, 1 H), 6.26 (d, J = 5.5 Hz, 1 H), 6.14 (d, J = 5.5 Hz, 1 H), 5.60 (br t, J = 5.5 Hz, 1 H), 5.17 (br t, J = 5.5 Hz, 1 H), 2.07 (s, 3 H), 2.00 (dt, J = 7.3, 14.6 Hz, 1 H), 1.96 (dt, J = 4.2, 14.6 Hz, 1 H). ¹³C NMR (CDCl₃): δ = 170.79, 154.52, 134.60, 134.39, 133.61, 128.37, 122.34, 114.99, 113.00, 81.34, 76.55, 38.00, 21.07. IR (ATR): 1733, 1584, 1573, 1474, 1442, 1366, 1085, 1029, 895, 748, 627 cm^-1. MS (EI): m/z (%rel intensity) = 296 (0.02) [M⁺], 43 (base peak). Anal. Calcd for C₁₃H₁₃BrO₃: C, 52.55; H, 4.41. Found: C, 52.37; H, 4.37.
1-Acetoxy-4-(2,6-dimethylphenoxy)-2-cyclopentene (6e): [α]_D ²⁷ -41.4 (c = 1.1, CHCl₃). ¹H NMR (CDCl₃): δ = 7.02 (d, J = 7.3 Hz, 2 H), 6.92 (t, J = 7.3 Hz, 1 H), 6.16 (d, J = 5.4 Hz, 1 H), 6.05 (d, J = 5.4 Hz, 1 H), 5.52 (br t, J = 4.4 Hz, 1 H), 4.81 (br t, J = 6.3 Hz, 1 H), 2.88 (dt, J = 7.3, 14.6 Hz, 1 H), 2.30 (s, 6 H), 2.09 (s, 3 H), 2.06 (dt, J = 4.4, 14.6 Hz, 1 H). ¹³C NMR (CDCl₃): δ = 171.09, 155.79, 136.60, 133.37, 131.06, 129.16, 123.95, 84.66, 76.73, 38.51, 21.39, 17.46. IR (ATR): 1730, 1365, 1237, 1198, 1091, 903, 730, 649, 630 cm^-1. MS (EI): m/z (%rel intensity) = 246 (0.09) [M⁺], 43 (base peak). HRMS (EI): m/z [M⁺] calcd for C₁₅H₁₈O₃: 246.1256; found: 246.1251. The enantiomeric excess was determined by HPLC analysis using a chiral stationary phase column [Chiralcel OD-H, eluent: n-hexane-2-propanol, 50:1; flow rate: 0.5 mL/min; t _R (major isomer) = 14.73 min and t _R (minor isomer) = 13.98 min] to be 90% ee.
1-Acetoxy-4-(3-methoxyphenoxy)-2-cyclopentene (6f): [α]_D ²⁶ +57.5 (c = 1.1, CHCl₃); 96% ee. ¹H NMR (CDCl₃): δ = 7.18 (t, J = 8.5 Hz, 1 H), 6.52 [td, J = 2.4, 8.5 Hz (overlapped), 2 H], 6.48 (t, J = 2.4 Hz, 1 H), 6.24 (d, J = 5.5 Hz, 1 H), 6.13 (d, J = 5.5 Hz, 1 H), 5.60 (br, 1 H), 5.16 (br, 1 H), 3.78 (s, 3 H), 2.96 (dt, J = 7.3, 14.6 Hz, 1 H), 2.05 (s, 3 H), 1.88 (dt, J = 3.9, 14.6 Hz, 1 H). ¹³C NMR (CDCl₃): δ = 170.77, 160.87, 158.99, 134.98, 134.12, 129.95, 107.35, 106.54, 101.88, 79.62, 55.24, 37.90, 21.04. IR (ATR): 1733, 1602, 1491, 1366, 1235, 1199, 1150, 1087, 1015, 891, 837, 765, 687, 629 cm^-1. MS (EI): m/z (%rel intensity) = 248 (1) [M⁺], 43 (base peak). Anal. Calcd for C₁₄H₁₆O₄: C, 67.73; H, 6.50. Found: C, 67.51; H, 6.45.
1-Acetoxy-4-(4-tert-buthylphenoxy)-2-cyclopentene (6g): [α]_D ²⁷ +148.7 (c = 1.4, CHCl₃); 94% ee. ¹H NMR (CDCl₃): δ = 7.30 (d, J = 8.5 Hz, 2 H), 6.85 (d, J = 8.5 Hz, 2 H), 6.24 (d, J = 5.5 Hz, 1 H), 6.11 (d, J = 5.5 Hz, 1 H), 5.60 (s, 1 H), 5.14 (s, 1 H), 2.96 (dt, J = 7.3, 14.6 Hz, 1 H), 2.05 (s, 3 H), 1.89 (dt, J = 3.9, 14.6 Hz, 1 H), 1.37 (s, 9 H). ¹³C NMR (CDCl₃): δ = 170.79, 155.51, 143.66, 135.25, 133.90, 126.30, 114.78, 79.61, 76.79, 37.98, 34.05, 31.48, 21.08. IR (ATR): 1736, 1511, 1365, 1232, 1185, 1087, 1013, 898, 829, 732, 630 cm^-1. MS (EI): m/z (%rel intensity) = 274 (0.2) [M⁺], 43 (base peak). Anal. Calcd for C₁₇H₂₂O₃: C, 74.42; H, 8.08. Found: C, 74.56; H, 8.22.
1-Acetoxy-4-phenoxy-2-cyclohexene (7): ¹H NMR (CDCl₃): δ = 7.26-7.31 (m, 2 H), 6.92-6.97 (m, 3 H), 6.08 (ddd, J = 1.2, 3.7, 10.0 Hz, 1 H), 6.07 (ddd, J = 1.2, 3.0, 10.0 Hz, 1 H), 5.25 (br s, 1 H), 4.76 (br s, 1 H), 2.07 (s, 3 H), 1.87-2.02 (m, 4 H). ¹³C NMR (CDCl₃): δ = 170.72, 157.52, 131.10, 129.59, 121.06, 115.84, 70.27, 67.38, 24.92, 24.75, 21.27. IR (ATR): 1730, 1597, 1492, 1371, 1226, 1079, 1035, 958, 903, 754, 692 cm^-1. MS (EI): m/z = 232 [M⁺]. The enantiomeric excess was determined by HPLC analysis using a chiral stationary phase column [Chiralcel OD-H, eluent: n-hexane-2-propanol, 50:1; flow rate: 0.5 mL/min; t _R (major isomer) = 21.33 min and t _R (minor isomer) = 18.48 min] to be 95% ee.