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Synlett 2009(18): 2924-2926  
DOI: 10.1055/s-0029-1218270
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Stereoselective Total Synthesis of (-)-(6R,11R,14R)-Colletallol via RCM Protocol

Palakodety Radha Krishna*, D. Venkata Ramana, B. Karunakar Reddy
D-211, Discovery Laboratory, Organic Chemistry Division-III, Indian Institute of Chemical Technology, Hyderabad- 500607, India
Fax: +91(40)27193158; e-Mail: prkgenius@iict.res.in;
Further Information

Publication History

Received 21 August 2009
Publication Date:
02 October 2009 (online)

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Abstract

The total synthesis of (-)-colletallol via a ring-closing metathesis protocol is reported.

Key words

(-)-colletallol - ring-closing metathesis (RCM) - Grubbs II catalyst - Jacobsen’s hydrolytic kinetic resolution (HKR)

    References and Notes

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13

Spectral Data for Selected Compounds Compound 5: colorless liquid; [α]D ²5 +243.0 (c 0.15, CHCl3). ¹H NMR (500 MHz, CDCl3): δ = 5.73-5.58 (m, 1 H), 5.24-5.13 (m, 2 H), 4.64 (d, J = 6.8 Hz, 1 H), 4.48 (d, J = 6.8 Hz, 1 H), 4.04-3.96 (m, 1 H), 3.83-3.73 (m, 1 H), 3.35 (s, 3 H), 1.68-1.39 (m, 4 H), 1.17 (d, J = 6.0 Hz, 3 H). ¹³C NMR (75 MHz, CDCl3): δ = 138.0, 117.2, 93.7, 77.4, 67.8, 55.4, 34.7, 31.7, 23.4. MS (EI): m/z = 113 [M - OMOM].
Compound 3: colorless liquid; [α]D ²5 +90.0 (c 0.25, CHCl3). ¹H NMR (500 MHz, CDCl3): δ = 7.19 (d, J = 8.3 Hz, 2 H), 6.94-6.85 (m, 1 H), 6.80 (d, J = 8.3 Hz, 2 H), 5.80 (d, J = 15.6 Hz, 1 H), 5.67-5.57 (m, 1 H), 5.23-5.13 (m, 2 H), 4.98-4.90 (m, 1 H), 4.67-4.61 (m, 1 H), 4.49-4.24 (m, 2 H), 4.37 (d, J = 11.2 Hz, 1 H), 3.98-3.90 (m, 1 H), 3.78 (s, 3 H), 3.63-3.56 (m, 1 H), 3.3 (s, 3 H), 2.49-2.4 (m, 1 H), 2.37-2.27 (m, 1 H), 1.67-1.54 (m, 4 H), 1.24 (d, J = 5.8 Hz, 3 H), 1.18 (d, J = 6.3 Hz, 3 H). ¹³C NMR (75 MHz, CDCl3): δ = 165.9, 145.1, 137.9, 129.0, 123.5, 117.4, 113.7, 93.6, 77.0, 73.1, 70.6, 70.1, 55.3, 55.2, 39.2, 31.7, 31.1, 19.9, 19.6. HRMS: m/z calcd for C23H34O6Na [M + Na]+: 429.2253; found: 429.2263.
Compound 2: colorless liquid; [α]D ²5 +155.9 (c 0.5, CHCl3). ¹H NMR (500 MHz, CDCl3): δ = 6.92-6.84 (m, 1 H), 6.39 (d, J = 17.0 Hz, 1 H), 6.09 (d, J = 17.0, 10.2 Hz, 1 H), 5.90-5.80 (m, 2 H), 5.70-5.61 (m, 1 H), 5.24-5.17 (m, 2 H), 5.12-5.06 (m, 1 H), 4.99-4.93 (m, 1 H), 4.68 (d, J = 6.8 Hz, 1 H), 4.52 (d, J = 6.8 Hz, 1 H), 4.00-3.94 (m, 1 H), 3.36 (s, 3 H), 2.55-2.44 (m, 2 H), 1.69-1.55 (m, 4 H), 1.28 (d, J = 6.3 Hz, 3 H), 1.24 (d, J = 6.3 Hz, 3 H). ¹³C NMR (75 MHz, CDCl3): δ = 165.7, 165.5, 143.2, 137.9, 130.7, 128.5, 124.5, 117.5, 93.7, 77.0, 71.4, 69.3, 55.4, 38.3, 31.7, 31.2, 20.3, 19.6. HRMS: m/z calcd for C18H28O6Na [M + Na]+: 363.1783; found: 363.1773.
Compound 11: brown colored liquid; [α]D ²5 +123.8 (c 0.06, CHCl3). ¹H NMR (500 MHz, CDCl3): δ = 6.75-6.71 (dd, J = 16.1, 5.4 Hz, 1 H), 6.70-6.63 (m, 1 H), 5.82 (d, J = 16.1 Hz, 1 H), 5.71 (d, J = 15.6 Hz, 1 H), 5.28-5.22 (m, 1 H), 5.16-5.11 (m, 1 H), 4.56 (s, 2 H), 4.44-4.40 (m, 1 H), 3.32 (s, 3 H), 2.54-2.48 (m, 2 H), 2.05-1.97 (m, 2 H), 1.81-1.74 (m, 1 H), 1.67-1.61 (m, 1 H), 1.45 (d, J = 6.3 Hz, 3 H), 1.17 (d, J = 6.8 Hz, 3 H). ¹³C NMR (75 MHz, CDCl3): δ = 168.3, 165.5, 149.2, 143.6, 126.2, 122.1, 94.5, 74.0, 69.1, 68.3, 55.4, 40.6, 27.7, 26.5, 20.7, 17.5. HRMS: m/z calcd for C16H24O6Na [M + Na]+: 335.1470; found: 335.1475.
Compound 1: colorless syrup; [α]D ²5 -85.5 (c 0.1 CHCl3). ¹H NMR (500 MHz, CDCl3): δ = 6.81 (dd, J = 15.6, 4.3 Hz, 1 H), 6.75-6.68 (m, 1 H), 5.87 (dd, J = 16.1, 1.4 Hz, 1 H), 5.79 (d, J = 15.1 Hz, 1 H), 5.26-5.16 (m, 2 H), 4.60 (s, 1 H), 2.53 (m, 1 H), 2.38-2.24 (m, 2 H), 2.17 (d, J = 2.9 Hz, 1 H), 1.79-1.67 (m, 2 H), 1.36 (d, J = 6.3 Hz, 3 H), 1.19 (d, J = 6.8 Hz, 3 H). ¹³C NMR (75 MHz, CDCl3): δ = 170.0, 165.6, 150.9, 143.5, 126.2, 121.3, 70.4, 69.1, 68.4, 40.6, 32.2, 29.1, 20.6, 17.4. HRMS: m/z calcd for C14H20O5Na [M + Na]+: 291.1208; found: 291.1210.