A Short and General Approach to the Synthesis of Styryllactones:(+)-Goniodiol, its Acetates and β-Trifluoromethyl Derivative, (+)-7-epi-Goniodiol and (+)-9-Deoxygoniopypyrone

Abstract

(+)-Goniodiol, its acetates and β-trifluoromethyl derivative, (+)-7-epi-Goniodiol and (+)-9-deoxygoniopypyrone, the representatives of styryllactones have been synthesized in a short and general way. The key steps involve the regioselective asymmetric dihydroxylation and the palladium-catalyzed cross-coupling of cyclic allylic carbonate with vinyltributylstannane.

Key words

(+)-Goniodiol - styryllactones - synthesis - asymmetric dihydroxylation - cross-coupling

References

• 1a Wu YC. Duh CY. Chang FR. Wang SK. Chang JJ. McPhail DR. McPhail AT. Lee KH. J. Nat. Prod.  1991,  54:  1077 
• 1b Sam TW. Saw-Yeu C. Matsjeh S. Gan EK. Razak D. Mohamed AL. Tetrahedron Lett.  1987,  28:  2541 
• 1c Talapatra SK. Basu D. Goaiwami S. Talapatra B. Indian J. Chem., Sect. B  1985,  24:  29 
• 2a Fang XP. Anderson JE. Qui XX. Kozlowski JF. McLaughlin JL. Tetrahedron  1993,  49:  1563 ; and references cited therein
• 2b Fang XP. Anderson JE. Chang CJ. McLaughlin JL. J. Nat. Prod.  1991,  54:  1034 
• 3a Tsubiki M. Kanai K. Honda T. J. Chem. Soc., Chem. Commun.  1992,  1640 
• 3b Yang Z.-C. Zhou W.-S. Heterocycles  1997,  45:  367 
• 3c Mukai C. Hirai S. Hanaoka M. J. Org. Chem.  1997,  62:  6619 
• 3d Surivet JP. Goré J. Vatèle JM. Tetrahedron  1996,  37:  14877 
• 3e Gillhouly JG. Tony Shing KM. J. Chem. Soc., Chem. Commun.  1988,  976 
• 3f Tsubuki M. Kanai K. Nagase H. Honda T. Tetrahedron  1999,  55:  2493 
• 3g Surivet JP. Vatèle JM. Tetrahedron Lett.  1998,  39:  7299 
• 4a Gesson JP. Jacquesy JC. Mondon M. Tetrahedron Lett.  1987,  28:  3949 
• 4b Somfai P. Tetrahedron  1994,  50:  11315 
• 5a Vanhessche Koen PM. Sharpless KB. J. Org. Chem.  1996,  61:  7978 
• 5b Becker H. King SB. Taniguchi M. Vanhessche Koenraad PM. Sharpless KB. J. Org. Chem.  1995,  60:  3940 
• 5c Colb HC. Van Nieuwenhze MS. Sharpless KB. Chem. Rev.  1994,  94:  2483 
• 5d Crispino GA. Jeong KS. Kolb HC. Wang Z.-M. Xu D. Sharpless KB. J. Org. Chem.  1993,  58:  3785 
• 6 Grummitt O. Becker EI. Org. Synth., Coll. Vol. IV   Wiley and Sons; New York: 1963.  p.771 
• 8 Quintard JP. Pereyre M. J. Organomet. Chem.  1972,  42:  75 
• 9 Kang SK. Yamaguchi T. Kim JS. Choi SC. Synth. Commun.  1997,  27:  1267 
• 11a Welch JT. Tetrahedron  1987,  43:  3123 
• 11b Organofluorine Chemistry, Principles and Chemical Applications   Banks BE. Smart BE. Tatlow JC. Plenum Press; New York: 1994. 
• 11c Biochemical Aspects of Fluorine Chemistry, Filler R., Kobayashi Y.   Elsevier Biomedical Press and Kodansha, LTD; Amsterdam: 1982. 
• 12 Hamper BC. Org. Synth.  1991,  70:  246 
• 13 Qing FL. Zhang YM. Tetrahedron Lett.  1997,  38:  6729 
• 15 Wu YC. Chang FR. Dun CY. Wang SK. Wu TS. Phytochemistry  1992,  31:  2851 
• 16 Yang ZC. Zhou WS. J. Chem. Soc., Chem. Commun.  1995,  743 
• 17 Mu Q. Tang W. Li C. Lu Y. Sun H. Zheng X. Wu N. Lou B. Xu B. Heterocycles  1999,  12:  2969 

7

The enantiomeric excess was determined by HPLC analysis on chiralcel OB-H, column (detected at 254 nm; eluent: hexane/i-PrOH).

3b (1-Phenyl-but-3-ene-1,2-diol) for (1 S , 2 S ): [α]_D ²⁰ -9.7 to 10.3 (c 0.7, CHCl₃). (1 R , 2 R ): [α]_D ²⁰ +10.6 to 11.1 (c 0.3, CHCl₃). IR (neat): 3390, 3087, 3032, 1645, 1604, 1495, 1454, 1198, 1126, 1054, 997, 928, 843, 763 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 7.35 (s, 5 H), 5.7 (m, 1 H), 5.25 (dd, J = 3.0 Hz, J = 15.8 Hz, 1 H), 5.15 (dd. J = 3 Hz, J = 10 Hz, 1 H), 4.5 (d, J = 7 Hz, 1 H), 4.2 (m, ???H), 3.0 (s, 1 H), 2.7 (s, 1 H). MS (EI): m/z = 164 (M, 7.88), 146 (M - 18, 1.50), 114 (71.83), 107(100), 79 (68.72). HRMS for C₁₀H₁₂O₂: 164.0838. E. A for C₁₀H₁₂O₂: C, 72.99%; H, 7.27%.
3c (4-Phenyl-but-3-ene-1,2-diol) for (2 R ): [α]_D ²⁴ -38.4 (c 1.8, CHCl₃). (2 S ): [α]_D ²⁴ +36.4 (c 1.45, CHCl₃). IR (neat): 3341, 3066, 3036, 1638, 1495, 1128, 1087, 942, 813, 751 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 7.37 (s, 5 H), 5,74 (d, 1 H, J = 12.6 Hz), 5.87 (dd, 1 H, J = 12.6 Hz, J = 7.4 Hz), 4.26 (m, 1 H), 3.75 (d, 2 H, J = 6.5 Hz), 3.1 (br, s, 1 H), 2.6 (br, s, 1 H). MS (EI) m/z = 164 (M, 7.88), 146 (M - 18, 1.50), 114 (71.83), 91(100), 79 (68.72). HRMS: Calcd for C₁₀H₁₂O₂: 164.0838. E. A. for C₁₀H₁₂O₂: C, 72.92%; H, 7.18%.

10

The ratio of E/Z was checked by GC-MS.

14

16, β-Trifluoromethylgoniodiol: [α]_D ²⁰ +68.2 (c 1.0, CHCl₃). MS (EI): m/z: 326 (M⁺ + 23). ¹H NMR (300 MHz, CDCl₃): δ = 7.3-7.5 (m, 5 H), 6.4 (s, 1 H), 5.3 (d, J = 7.2 Hz, 1 H), 4.8 (dd, J = 7.2, 5.8 Hz, 1 H), 4.2 (m, 1 H).