Stereoselective Total Synthesis of (+)-Sapinofuranone B

Abstract

A stereoselective total synthesis of sapinofuranone B is described starting from commercially available l-(+)-diethyl tartrate using a ring-opening reaction, a Mitsunobu inversion, and a Sonogashira coupling as the key steps.

Key words

ring-opening - Mitsunobu - acetonide - Sonogashira - γ-lactones

References and Notes

• 1a Ling R. Yoshida M. Mariano PS. J. Org. Chem.  1996,  61:  4439 
• 1b Kiyota H. Shi Q.-W. Oritani T. Nat. Prod. Lett.  2007,  16:  21 
• 1c Cho KW. Lee H.-S. Rho J.-R. Kim T.-S. Mo SJ. Shin J. J. Nat. Prod.  2001,  64:  664 
• 1d Gunasekera SP. Isbrucker RA. Longley RE. Wright AE. Pomponi SA. Reed JK. J. Nat. Prod.  2004,  67:  110 
• 2 Clough S. Raggatt ME. Simpson TJ. Willis CL. Whiting A. Wrigley SK. J. Chem. Soc., Perkin Trans. 1  2000,  2475 
• 3 Evidente A. Sparapano L. Fierro O. Bruno G. Motta A. J. Nat. Prod.  1999,  62:  253 
• 4a Kumar P. Naidu VS. Gupta P. J. Org. Chem.  2005,  70:  2843 
• 4b Kutsumura N. Yokoyama T. Ohgiya T. Nishiyama S. Tetrahedron Lett.  2006,  47:  4133 
• For our contributions on lactone-containing molecules, see:
• 5a Srihari P. Vijaya Bhasker E. Bal Reddy A. Yadav JS. Tetrahedron Lett.  2009,  50:  2420 
• 5b Srihari P. Kumar BP. Subbarayudu P. Tetrahedron Lett.  2007,  48:  6997 
• 5c Sabitha G. Gopal P. Synth. Commun.  2007,  37:  1495 
• 5d Srihari P. Bhasker EV. Harshavardhan SJ. Yadav JS. Synthesis  2006,  4041 
• 5e Sabitha G. Bhaskar V. Yadav JS. Tetrahedron Lett.  2006,  47:  8179 
• 5f Yadav JS. Prathap I. Padmaja TB. Tetrahedron Lett.  2006,  47:  3773 
• 5g Yadav JS. Reddy MS. Prasad AR. Tetrahedron Lett.  2005,  46:  2133 
• 5h Yadav JS. Rao KV. Reddy MS. Prasad AR. Tetrahedron Lett.  2006,  47:  4393 
• 5i Yadav JS. Raju AK. Rao PP. Rajaiah G. Tetrahedron: Asymmetry  2005,  16:  3283 
• 5j Yadav JS. Reddy KB. Sabitha G. Tetrahedron Lett.  2004,  45:  6475 
• 5k Yadav JS. Reddy MS. Prasad AR. Tetrahedron Lett.  2005,  46:  2133 
• For our contributions on macro-lactones, see:
• 5l Yadav JS. Pratap TV. Rajender V. J. Org. Chem.  2007,  72:  5882 
• 5m Yadav JS. Srihari P. Tetrahedron: Asymmetry  2004,  15:  81 
• 6a Seebach D. Hungerbuhler Modern Synthetic Methods   Vol. 2:  Scheffold R. Salle and Sauerlander-Verlag; Frankfurt and Aarau: 1980.  p.91-171  
• 6b Iida H. Yamazaki N. Kibayashi C. J. Org. Chem.  1987,  52:  3337 
• 7a Tidwell TT. Synthesis  1990,  857 
• 7b Tidwell TT. Org. React.  1990,  39:  297 
• 8a Mulzer J. Kappert M. Huttner G. Jibril I. Angew. Chem.  1984,  96:  726 
• 8b Mulzer J. Kappert M. Huttner G. Jibril I. Angew. Chem. Int. Ed. Engl.  1984,  23:  704 
• 9 Furstner A. Fenster MDB. Fasching B. Godbout C. Radkowski K. Angew. Chem.  2006,  118:  5632 
• 10a Yadav JS. Chander MC. Joshi BV. Tetrahedron Lett.  1988,  29:  2737 
• 10b Yadav JS. Bandyopadhyay A. Kunwar AC. Tetrahedron Lett.  2001,  42:  4907 
• 10c Yadav JS. Abraham S. Reddy MM. Sabitha G. Sankar AR. Kunwar AC. Tetrahedron Lett.  2001,  42:  4713 
• 10d Yadav JS. Ahmed M. Tetrahedron Lett.  2002,  43:  7147 
• 11 Mitsunobu O. Synthesis  1981,  1 
• 12 Charette AB. Cote B. J. Am. Chem. Soc.  1995,  117:  12721 
• 13a Sonogashira K. Tohda Y. Hagihara N. Tetrahedron Lett.  1975,  4467 
• 13b Yu Q. Wu Y. Ding H. Wu Y.-L.
  J. Chem. Soc., Perkin Trans. 1  1999,  1183 
• 13c Madec D. Ferezou J.-P. Tetrahedron Lett.  1997,  38:  6661 
• 13d Izzo I. Decaro S. De Riccardis F. Spinella A. Tetrahedron Lett.  2000,  41:  3975 
• 14 Boland W. Schroer N. Sieler C. Helv. Chim. Acta  1987,  70:  1025 

15

Spectroscopic data for selected compounds. Compound 3: [α] _d ^²8 +20.1 (c 0.53, CHCl₃) {Lit.^² +19.0 (c 0.77, CHCl₃)}. ^¹H NMR (500 MHz, CDCl₃): δ = 1.80 (dd, J = 6.6 Hz, 3 H), 1.94-2.37 (m, 2 H), 2.45-2.69 (m, 2 H), 4.46 (dd, J = 6.8, 12.8 Hz, 1 H), 4.57 (dd, J = 5.8, 8.8 Hz, 1 H), 5.30 (t, J = 10.0 Hz, 1 H), 5.85 (qd, J = 6.9, 13.9 Hz, 1 H), 6.19 (t, J = 11.0 Hz, 1 H), 6.28-6.42 (m, 1 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 18.4, 23.7, 28.4, 70.1, 82.8, 123.9, 126.0, 133.8, 133.9, 177.0. IR (neat): 3383, 2924, 2854, 1767, 1460, 1184, 1039 cm^-¹. MS (LC-MS): m/z = 205 [M + Na]⁺. HRMS:
m/z calcd for C₁₀H₁₄NaO₃: 205.0849; found: 205.0840. Compound 7: [α] _d ^²5 +18.7 (c 1.2, CHCl₃). ^¹H NMR (300 MHz, CDCl₃): δ = 1.54-1.84 (m, 4 H), 2.39 (d, J = 2.2 Hz, 1 H), 3.33 (s, 3 H), 3.46-3.60 (m, 5 H), 4.10-4.27 (m, 2 H), 4.56 (s, 2 H), 4.71 (Abq, J = 7.2 Hz, 2 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 25.8, 28.5, 55.1, 56.0, 65.1, 67.3, 74.1, 81.7, 84.6, 96.3, 97.8. IR (neat): 3418, 3279, 2937, 2150, 1646, 1447, 1381, 1150, 1106, 1037, 917 cm^-¹. MS (LC-MS): m/z = 255 [M + Na]⁺. HRMS: m/z calcd for C₁₁H₂₀NaO₅: 255.1208; found: 255.1203. Compound 11: [α] _d ^²5 +8.0 (c 1.0, CHCl₃). ^¹H NMR (200 MHz, CDCl₃): δ = 0.10 (s, 6 H), 0.91 (s, 9 H), 1.35 (s, 3 H), 1.37 (s, 3 H), 2.14-2.23 (m, 1 H), 2.40-2.49 (m, 1 H), 2.90 (br s, 1 H, OH), 3.59-3.70 (m, 3 H), 3.81-3.90 (m, 2 H), 5.07-5.16 (m, 2 H), 5.82-5.96 (m, 1 H). ^¹³C NMR (75 MHz, CDCl₃): δ = -5.5, 18.3, 25.8, 26.8, 26.9, 37.8, 64.2, 71.5, 79.5, 81.6, 108.8, 117.5, 134.5. IR (neat): 3447, 2932, 1617, 1379, 1254, 1082, 837, 774 cm^-¹. MS (LC-MS): m/z = 339 [M + Na]⁺. HRMS: m/z calcd for C₁₆H₃₂SiNaO₄: 339.1967; found: 339.1970