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. 2006 Mar 8;128(9):2796-7.
doi: 10.1021/ja058692k.

Total synthesis of dolabelide D

Peter K Park  1 , Steven J O'Malley, Darby R Schmidt, James L Leighton
Affiliations

Total synthesis of dolabelide D

Peter K Park et al. J Am Chem Soc. .

Abstract

The first total synthesis of dolabelide D (or of any of the closely related dolabelides) has been achieved with a longest linear sequence of 17 steps. Key features of the synthesis include an application of the catalytic asymmetric silane alcoholysis, the tandem silylformylation-crotylsilylation, and a Brook-like 1,4-carbon to oxygen silyl migration.

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Figures

Scheme 1
Scheme 1
Scheme 2
Scheme 2
(a) 4 mol% CuCl, 4 mol% NaO-t-Bu, 4 mol% (R, R)-BDPP, PhH. (b) i. 2 mol% [Rh(acetone)2-(P(OPh)3)2]BF4, CO, PhH, 60 °C; ii. MeLi, Et2O −78 to 23 °C. (c) TESCl, Et3N, CH2Cl2, −20 °C. (d) n-BuLi, THF, −78 °C; CuBr•Me2S, DMPU, 23 °C; MeI, −78 to 23 °C. (e) 25 mol% PdCl2, CuCl, DMF, THF, H2O, O2. (f) Ac2O, pyridine, DMAP, CH2Cl2. (g) (+)-(ipc)2BCl, Et3N, 5-hexenal, Et2O −78 to 23 °C. (h) Me4NBH(OAc)3, AcOH, CH3CN, THF, −40 to −20 °C. (i) 1,1-dimethoxycyclopentane, PPTS, CH2Cl2. (j) n-Bu4NF, THF.
Scheme 3
Scheme 3
(a) 15, CH2Cl2, −20 °C. (b) NaH, PMBBr, THF, reflux, (c) 25 mol% PdCl2, CuCl, DMF, H2O, O2. (d) ent-19, CH2Cl2. (e) 2 mol% Rh(acac)(CO)2, 10 mol% PPh3, H2/CO, 2,2-dimethoxypropane, PPTS, 60 °C. (f) 9-BBN, THF, −78 to 23 °C; H2O2, NaOH. (g) (COCl)2, DMSO, Et3N, CH2Cl2, −78 °C. (h) NaClO2, NaH2PO4,2-methyl-2-butene, t-BuOH, H2O. (i) K2CO3, CH2=CHCH2Br, acetone, reflux, (j) PPTS, acetone, H2O, reflux, (k) n-Bu2BOTf, i-Pr2NEt, Et2O, −110 °C. (1) TESCl, imidazole, CH2Cl2. (m) L-Selectride, CH2Cl2, −78 °C. (n) Ac2O, pyridine, DMAP, CH2Cl2. (o) 10 mol% Pd(PPh3)4, morpholine, THF.
Scheme 4
Scheme 4
(a) Et3N, DMAP, toluene, −78 to 0 °C. (b) PPTS, MeOH. (c) DDQ, CH2Cl2, pH 7 buffer, (d) 25 mol% 31, CH2Cl2, reflux.
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