Total Synthesis of (+)-Cardiobutanolide
through a Carbohydrate-Based Approach

J. S. Yadav; B. Madhavarao; K. Sanjeeva Rao

doi:10.1055/s-0029-1218344

LETTER

Total Synthesis of (+)-Cardiobutanolide through a Carbohydrate-Based Approach

J. S. Yadav*, B. Madhavarao, K. Sanjeeva Rao
Division of Organic Chemistry, Indian Institute of Chemical Technology, Hyderabad 500 007, India
Fax: +91(40)27160512; e-Mail: yadavpub@iict.res.in;

Abstract

All articles of this category

Abstract

The naturally occurring styryllactone (+)-cardiobutanolide has been synthesized in a highly efficient manner using d-glucono-δ-lactone, as a chiral pool starting material. The synthesis involves the stereoselective addition of Grignard reagent to a chiral aldehyde, zinc-mediated reductive deoxygenation of 4-alkoxybut- 2-enoic acid moiety and asymmetric dihydroxylation as the key steps.

Key words

cardiobutanolide - δ-gluconolactone - chiron approach - reductive elimination process - asymmetric dihydroxylation

Full Text

References

References and Notes

<A NAME="RD16709ST-1A">1a</A> Cave A. Figadere B. Laurens A. Cortes D. Prog. Chem. Org. Nat. Prod. 1997, 70: 81

<A NAME="RD16709ST-1B">1b</A> Zafra-Polo MC. Figadere B. Gallardo T. Tormo JR. Cortes D. Phytochemistry 1998, 48: 1087

<A NAME="RD16709ST-1C">1c</A> Alali FQ. Liu XX. Mclaughlin JL. J. Nat. Prod. 1999, 62: 504

<A NAME="RD16709ST-2">2</A> Mondon M. Gesson J.-P. Curr. Org. Synth. 2006, 3: 175

<A NAME="RD16709ST-3">3</A> Hisham A. Toubi M. Shuaily W. Bai MDA. Fujimoto Y. Phytochemistry 2003, 62: 597

<A NAME="RD16709ST-4A">4a</A> Ruiz P. Murga J. Carda M. Marco JA. J. Org. Chem. 2005, 70: 713

<A NAME="RD16709ST-4B">4b</A> Krishna PR. Reddy PVN. Tetrahedron Lett. 2006, 47: 4627

<A NAME="RD16709ST-4C">4c</A> Prasad KR. Gholap SL. J. Org. Chem. 2008, 73: 2916

<A NAME="RD16709ST-5A">5a</A> Garg A. Singh RP. Singh VK. Tetrahedron 2006, 62: 11240

<A NAME="RD16709ST-5B">5b</A> Matsuura D. Takabe K. Yoda H. Tetrahedron Lett. 2006, 47: 1371

<A NAME="RD16709ST-6A">6a</A> Yadav JS. Rao BM. Sanjeevarao K. Reddy BVS. Synlett 2008, 1039

<A NAME="RD16709ST-6B">6b</A> Yadav JS. Rao BM. Sanjeevarao K. Tetrahedron: Asymmetry 2009, 20: 1725

<A NAME="RD16709ST-7">7</A> Yadav JS. Barma DK. Tetrahedron 1996, 52: 4457

<A NAME="RD16709ST-8">8</A> Rao KS. Reddy DS. Mukkanti K. Pal M. Iqbal J. Tetrahedron Lett. 2006, 47: 6623

<A NAME="RD16709ST-9">9</A> Surivet J.-P. Vatele J.-M. Tetrahedron 1999, 55: 13011

Compound 5: [α]_D ^²5 +18.4 (c 1.0, CHCl₃). ^¹H NMR (CDCl₃, 300 MHz): δ = 1.08, 1.19, 1.22, 1.29 (5 × s, 21 H), 3.66-3.81 (m, 3 H), 3.86-3.93 (m, 2 H), 4.79 (d, J = 5.28 Hz, 1 H), 7.16-7.26 (m, 6 H), 7.28-7.43 (m, 7 H), 7.73 (d, J = 6.04 Hz, 2 H). ^¹³C NMR (CDCl₃, 75 MHz): δ = 19.6, 25.5 (3 C), 26.3 (2 C), 27.3 (2 C), 65.5, 76.3, 77.1, 77.7, 83.0, 109.3, 110.3, 127.5 (2 C), 127.6 (2 C), 128.0, 128.1 (2 C), 129.7 (2 C), 129.9 (2 C), 133.5, 133.9, 136.3 (2 C), 136.4 (2 C), 140.0. IR (KBr): 3436, 2998, 2872, 1375, 1160, 1071, 842, 703 cm^-¹. HRMS: m/z [M + Na]⁺ calcd for C₃₃H₄₂O₅: 415.2440; found: 415.2442.
Compound 7: ^¹H NMR (CDCl₃, 300 MHz): δ = 1.07 (s, 9 H), 1.25 (s, 3 H), 1.29 (s, 3 H), 1.35-1.30 (m, 3 H), 3.02 (s, 1 H, OH), 3.67-3.71 (m, 1 H), 4.17-4.28 (m, 3 H), 4.79 (d, J = 5.28 Hz, 1 H), 7.14-7.28 (m, 8 H), 7.34-7.41 (m, 5 H), 7.69 (d, J = 6.78 Hz, 2 H). ^¹³C NMR (CDCl₃, 75 MHz): δ = 14.2, 19.35, 25.6 (3 C), 26.4 (2 C), 60.13, 62.13, 70.65, 74.25, 77.3, 79.75, 81.73, 108.75, 126.0, 128.1 (2 C), 128.6 (4 C), 129.3, 130.1 (4 C), 134.77 (2 C), 135.99 (2 C), 139.1 (2 C), 168.24. LCMS: m/z = 595 [M + Na]⁺.Compound 8: ^¹H NMR (CDCl₃, 300 MHz): δ = 1.06 (s, 9 H), 1.24 (s, 3 H), 1.28 (s, 3 H), 1.32-1.37 (m, 3 H), 3.68-3.72 (m, 1 H), 3.83-3.87 (m, 1 H), 4.18-4.30 (m, 3 H), 4.79 (d, J = 6.23 Hz, 1 H), 5.77 (dd, J = 1.88, 15.67 Hz, 1 H), 6.59 (dd, J = 4.15, 15.67 Hz, 1 H), 7.16-7.29 (m, 8 H), 7.36-7.43 (m, 5 H), 7.69 (d, J = 7.55 Hz, 2 H). ^¹³C NMR (CDCl₃, 75 MHz): δ = 14.2, 19.5, 25.62 (3 C), 26.50 (2 C), 60.45, 69.4, 71.62, 75.94, 78.63, 111.7, 121.14, 126.0, 128.1 (2 C), 128.4 (4 C), 128.6 (2 C), 130.14 (4 C), 134.73 (2 C), 130.90 (2 C), 139.14, 149.45, 167.8. LCMS: m/z = 597 [M + Na]⁺.
Compound 9: ^¹H NMR (CDCl₃, 300 MHz): δ = 1.03 (s, 9 H), 1.06 (s, 3 H), 1.15 (s, 3 H), 1.29-1.32 (m, 3 H), 2.02 (s, 3 H), 3.66-3.70 (m, 1 H), 3.95-3.99 (m, 1 H), 4.09-4.21 (m, 3 H), 4.66 (d, J = 6.04 Hz, 1 H), 4.67 (dd, J = 5.85, 15.86 Hz, 1 H), 5.61 (dd, J = 1.32, 15.67 Hz, 1 H), 7.15-7.28 (m, 8 H), 7.30-7.38 (m, 5 H), 7.70 (d, J = 6.23 Hz, 2 H). ^¹³C NMR (CDCl₃, 75 MHz): δ = 13.98, 19.13, 20.52, 22.45 (2 C), 26.84 (3 C), 60.27, 70.81, 76.57, 77.74, 80.44, 109.89, 122.82, 127.18 (2 C), 128.0 (4 C), 129.50, 132.94 (4 C), 133.32 (2 C), 135.80 (2 C), 139.13, 139.35 (2 C), 142.04, 165.29, 169.14. LCMS: m/z = 639 [M + Na]⁺.
Compound 10: [α]_D ^²5 +88.75 (c 1.0, CHCl₃). ^¹H NMR (CDCl₃, 300 MHz): δ = 1.05 (s, 3 H), 1.06 (s, 3 H), 1.13 (s, 9 H), 1.25 (t, J = 7.17 Hz, 3 H), 2.55-2.63 (m, 2 H), 3.62-3.67 (m, 1 H), 3.80-3.85 (m, 1 H), 4.15 (q, J = 7.17 Hz, 2 H), 4.70 (d, J = 6.42 Hz, 1 H), 5.58-5.64 (m, 1 H), 6.66-6.67 (m, 1 H), 7.22-7.46 (m, 13 H), 7.64 (d, J = 6.42 Hz, 2 H). ^¹³C NMR (CDCl₃, 75 MHz): δ = 14.22, 19.35, 25.51 (3 C), 26.90 (2 C), 34.53, 60.14, 75.68, 77.50, 81.45, 108.74, 126.19, 127.32 (2 C), 127.57, 127.84 (4 C), 129.88 (2 C), 130.12, 134.77 (4 C), 135.69 (2 C), 135.99 (2 C), 138.0, 168.0. IR (KBr): 3436, 2998, 2873, 1742, 1630, 1160, 1071, 843, 703 cm^-¹. HRMS: m/z [M + Na]⁺ calcd for C₃₄H₄₂O₅Si: 558.7824; found:558.7835.
Compound 11: [α]_D ^²5 +92.72 (c 1.0, CHCl₃). ^¹H NMR (CDCl₃, 300 MHz): δ = 1.05 (s, 3 H), 1.06 (s, 3 H), 1.13 (s, 9 H), 1.25 (t, J = 7.17 Hz, 3 H), 2.53-2.62 (m, 2 H), 3.60-3.67 (m, 2 H), 3.80-3.85 (m, 2 H), 4.15 (q, J = 7.17 Hz, 2 H), 4.70 (d, J = 6.42 Hz, 1 H), 7.22-7.46 (m, 13 H), 7.64 (d, J = 6.42 Hz, 2 H). ^¹³C NMR (CDCl₃, 75 MHz): δ = 14.22, 19.35, 25.60 (3 C), 26.85 (2 C), 35.34, 60.18, 68.41, 75.60, 77.40, 77.5, 81.45, 108.80, 126.20, 127.52 (2 C), 127.84 (2 C), 129.88 (4 C), 134.77 (4 C), 135.69 (2 C), 135.99 (2 C), 138.0, 168.42. IR (KBr): 3650, 3446, 2992, 2872, 1742, 1071, 843, 703 cm^-¹. HRMS: m/z [M + Na]⁺ calcd for C₃₄H₄₄O₇Si: 592.7932; found: 592.7943.
Compound 2: mp 192-193 ˚C (Lit.^³ 189-190 ˚C); [α]_D ^²5 +8.3 (c 0.4, MeOH). ^¹H NMR (CDCl₃, 300 MHz): δ = 2.38 (d, J = 16.6 Hz 1 H), 2.85 (m, 1 H), 3.94 (d, J = 6.1 Hz, 1 H), 4.41 (d, J = 7.4 Hz, 1 H), 4.54 (dd, J = 3.1, 6.7 Hz, 1 H), 4.63 (br s, 1 H), 4.79 (d, J = 7.5 Hz, 1 H), 7.21-7.32 (m, 4 H), 7.43 (d, J = 6.7 Hz, 1 H). ^¹³C NMR (CDCl₃, 75 MHz): δ = 39.0, 70.5, 71.5, 75.4, 76.1, 88.4, 127.1, 128.0, 129.7, 144.1, 176.0. IR (KBr): 3514, 3475, 2931, 2854, 1761, 1317, 1445, 1206 cm^-¹. HRMS: m/z [M + Na]⁺ calcd for C₁₃H₁₆O₆: 291.0846; found: 291.0843.