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

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Synlett 2008(10): 1557-1561
DOI: 10.1055/s-2008-1078422

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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;

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Publication History

Received 11 January 2008
Publication Date:
16 May 2008 (online)

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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

References and Notes

For reviews on aqueous-switching of organic transformations, see:
1a Li C.-J. Chan T.-H. Organic Reactions in Aqueous Media Wiley; New York: 1997.

Crossref PubMed Google Scholar
1b Grieco PA. Organic Synthesis in Water Kluwer Academic Publishers; Dordrecht: 1997.

Crossref PubMed Google Scholar
1c Herrmann WA. Kohlpaintner CW. Angew. Chem., Int. Ed. Engl. 1993, 32: 1524

Crossref PubMed Google Scholar
1d Lindström UM. Chem. Rev. 2002, 102: 2751

Crossref PubMed Google Scholar
For reviews on heterogeneous-switching of organic transformations, see:
2a Bailey DC. Langer SH. Chem. Rev. 1981, 81: 109

Crossref Google Scholar
2b Shuttleworth SJ. Allin SM. Sharma PK. Synthesis 1997, 1217

Crossref Google Scholar
2c Shuttleworth SJ. Allin SM. Wilson RD. Nasturica D. Synthesis 2000, 1035

Crossref Google Scholar
2d Dörwald FZ. Organic Synthesis on Solid Phase Wiley-VCH; Weinheim: 2000.

Crossref Google Scholar
2e Leadbeater NE. Marco M. Chem. Rev. 2002, 102: 3217

Crossref Google Scholar
2f 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

Crossref Google Scholar
2g McNamara CA. Dixon MJ. Bradley M. Chem. Rev. 2002, 102: 3275

Crossref Google Scholar
2h Chiral Catalyst Immobilization and Recycling De Vos DE. Vankelecom IFJ. Jacobs PA. Wiley-VCH; Weinheim: 2000.

Crossref Google Scholar
2i Fan Q.-H. Li Y.-M. Chan ASC. Chem. Rev. 2002, 102: 3385

Crossref Google Scholar
For recent reviews on solid-phase reactions using palladium catalysts, see:
3a 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.

PubMed Google Scholar
3b Uozumi Y. Top. Curr. Chem. 2004, 242: 77

PubMed Google Scholar
For studies on polymer-supported catalysts from the author’s group, see:
4a Cross-coupling: Uozumi Y. Danjo H. Hayashi T. J. Org. Chem. 1999, 64: 3384

Crossref Google Scholar
4b Carbonylation reaction: Uozumi Y. Watanabe T. J. Org. Chem. 1999, 64: 6921

Crossref Google Scholar
4c Michael addition: Shibatomi K. Nakahashi T. Uozumi Y. Synlett 2000, 1643

Crossref Google Scholar
Suzuki-Miyaura coupling:
4d Uozumi Y. Nakai Y. Org. Lett. 2002, 4: 2997

Crossref Google Scholar
4e Uozumi Y. Kikuchi M. Synlett 2005, 1775

Crossref Google Scholar
4f Heck reaction: Uozumi Y. Kimura T. Synlett 2002, 2045

Crossref Google Scholar
4g Rhodium catalysis: Uozumi Y. Nakazono M. Adv. Synth. Catal. 2002, 344: 274

Crossref Google Scholar
(Wacker cyclization):
4h Hocke H. Uozumi Y. Synlett 2002, 2049

Crossref Google Scholar
4i Hocke H. Uozumi Y. Tetrahedron 2003, 59: 619

Crossref Google Scholar
4j Sonogashira reaction: Uozumi Y. Kobayashi Y. Heterocycles 2003, 59: 71

Crossref Google Scholar
Oxidation:
4k Uozumi Y. Nakao R. Angew. Chem. Int. Ed. 2003, 42: 194

Crossref Google Scholar
4l Uozumi Y. Nakao R. Angew. Chem. 2003, 115: 204

Crossref Google Scholar
4m Yamada YMA. Arakawa T. Hocke H. Uozumi Y. Angew. Chem. Int. Ed. 2007, 46: 704

Crossref Google Scholar
4n Reduction: Nakao R. Rhee H. Uozumi Y. Org. Lett. 2005, 7: 163

Crossref Google Scholar
4o Alkylation: Yamada YMA. Uozumi Y. Org. Lett. 2006, 8: 1375

Crossref Google Scholar
For studies on π-allylic transformations with polymer-supported complex catalysts in water, see:
5a Uozumi Y. Danjo H. Hayashi T. Tetrahedron Lett. 1997, 38: 3557

Article in Thieme Connect Google Scholar
5b Danjo H. Tanaka D. Hayashi T. Uozumi Y. Tetrahedron 1999, 55: 14341

Article in Thieme Connect Google Scholar
5c Uozumi Y. Suzuka T. Kawade R. Takenaka H. Synlett 2006, 2109

Article in Thieme Connect Google Scholar
For studies on heterogeneous aquacatalytic asymmetric π-allylic transformations with polymer-supported complex catalysts in water, see:
6a Alkylation: Uozumi Y. Danjo H. Hayashi T. Tetrahedron Lett. 1998, 39: 8303

Crossref Google Scholar
6b Reduction with monodentate phosphine (MOP): Hocke H. Uozumi Y. Tetrahedron 2004, 60: 9297

Crossref Google Scholar
6c Alkylation: Uozumi Y. Shibatomi K. J. Am. Chem. Soc. 2001, 123: 2919

Crossref Google Scholar
6d Amination: Uozumi Y. Tanaka H. Shibatomi K. Org. Lett. 2004, 6: 281

Crossref Google Scholar
6e Cyclization: Nakai Y. Uozumi Y. Org. Lett. 2005, 7: 291

Crossref Google Scholar
6f Etherification: Uozumi Y. Kimura M. Tetrahedron: Asymmetry 2006, 17: 161

Crossref Google Scholar
6g Nitromethylation: Uozumi Y. Suzuka T. J. Org. Chem. 2006, 71: 8644

Crossref Google Scholar
6h Kobayashi Y. Tanaka D. Danjo H. Uozumi Y. Adv. Synth. Catal. 2006, 348: 1561

Crossref Google Scholar
6i Uozumi Y. Pure Appl. Chem. 2007, 79: 1481

Crossref Google Scholar
For recent reviews on asymmetric π-allylic substitution, see:
7a Acemoglu L. Williams JMJ. Handbook of Organopalladium Chemistry for Organic Synthesis Negishi E. de Meijere A. Wiley; New York: 2002.

Google Scholar
7b Trost BM. Crawley ML. Chem. Rev. 2003, 103: 2921

Google Scholar
8a Taniimori S. Tsuji Y. Kirihara M. Biosci., Biotechnol., Biochem. 2002, 66: 660

Google Scholar
8b Song ES. Yang JW. Roh EJ. Lee S.-G. Han H. Angew. Chem. Int. Ed. 2002, 41: 3852

Google Scholar
8c Trost BM. Van Vranken DL. Bingel C. J. Am. Chem. Soc. 1992, 114: 9327

Google Scholar
9d Trost B. M., Pulley S. R., Bingel C.; Tetrahedron Lett.; 1995, 36: 8737
13 Nishiyama H. Sakata N. Sugimoto H. Motoyama Y. Wakita H. Nagase H. Synlett 1998, 930

Article in Thieme Connect Google Scholar

10

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

11

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

12

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).

14

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] .

15

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.