Garner’s aldehyde as a versatile intermediate in the synthesis of enantiopure natural products
- Mikko Passiniemi and
- Ari M.P. Koskinen
Beilstein J. Org. Chem. 2013, 9, 2641–2659, doi:10.3762/bjoc.9.300
Graphical Abstract
Figure 1: Structures of limonene, carvone and thalidomide.
Figure 2: Structure of Garner’s aldehyde.
Scheme 1: (a) i) Boc2O, 1.0 N NaOH (pH >10), dioxane, +5 °C → rt; ii) MeI, K2CO3, DMF, 0 °C → rt (86% over tw...
Scheme 2: (a) AcCl, MeOH, 0 °C → reflux (99%); (b) i) (Boc)2O, Et3N, THF, 0 °C → rt → 50 °C (89%); ii) Me2C(O...
Scheme 3: (a) LiAlH4, THF, rt (93–96%); (b) (COCl)2, DMSO, iPr2NEt, CH2Cl2, −78 °C → −55 °C (99%).
Scheme 4: The Koskinen procedure for the preparation of Garner’s aldehyde. (a) i) AcCl, MeOH, 0 °C → 50 °C (9...
Scheme 5: Burke’s synthesis of Garner’s aldehyde. BDP - bis(diazaphospholane).
Figure 3: Structures of some iminosugars (7, 9), peptide antibiotics (8) and sphingosine (10) and pachastriss...
Scheme 6: Use of Garner’s aldehyde 1 in multistep synthesis.
Scheme 7: Explanation of the anti- and syn-selectivity in the nucleophilic addition reaction.
Scheme 8: Herold’s method: (a) Lithium 1-pentadecyne, HMPT, THF, −78 °C (71%); (b) Lithium 1-pentadecyne, ZnBr...
Scheme 9: (a) Ethyl lithiumpropiolate, HMPT, THF, −78 °C; (b) (S)- or (R)-MTPA, DCC, DMAP, THF, rt (18, 81%) ...
Scheme 10: Coleman’s selectivity studies and their transition state model for the co-ordinated delivery of the...
Scheme 11: (a) PhMgBr, THF, −78 °C → 0 °C [62] or (a) PhMgBr, Et2O, 0 °C [63].
Scheme 12: (a) cat. RhCl3·3H2O, cat. 26, NaOMe, Ph-B(OH)2, aq DME, 80 °C (24, 71%); (b) cat. RhCl3·3H2O, cat. ...
Scheme 13: Lithiated dithiane (3 equiv), CuI (0.3 equiv), BF3·Et2O (6 equiv), THF, −50 °C, 12 h (70%).
Scheme 14: Addition reaction reported by Lam et al. (a) 1-Hexyne, n-BuLi, THF, −15 °C or −40 °C.
Scheme 15: (a) n-BuLi, HMPT, toluene, −78 °C → rt (85%); (b) n-BuLi, ZnCl2, toluene/Et2O, −78 °C → rt (65%).
Scheme 16: (a) n-BuLi, 34, THF, −40 °C [69]; (b) n-BuLi, 35, THF, −78 °C → rt (80%) [70]; (c) n-BuLi, 35, HMPT, THF, −...
Scheme 17: (a) cat. Rh(acac)(CO)2, 42, THF, 40 °C (74%).
Scheme 18: (a) 1-PropynylMgBr, CuI, THF, Me2S, −78 °C (95%); (b) Ethynyltrimethylsilane, EtMgBr, CuI, THF, Me2...
Scheme 19: (a) cat. 50, toluene, 0 °C (52%); (b) cat. 51, toluene, 0 °C (51%); (c) cat. 52, toluene, 0 °C (50%...
Scheme 20: (a) (iPr)3SiH, cat. Ni(COD)2, dimesityleneimidazolium·HCl, t-BuOK, THF, rt.
Scheme 21: (a) Cp2Zr(H)Cl, cat. AgAsF6, CH2Cl2, rt; (b) Cp2Zr(H)Cl, 1-pentadecyne, cat. ZnBr2 in THF for anti-...
Scheme 22: (a) i) 31, n-BuLi, THF, −78 °C; ii) (S)-1, THF, −78 °C; (b) Red-Al, THF, 0 °C.
Scheme 23: (a) 61, n-BuLi, DMPU, toluene, −78 °C, then (S)-1, toluene, −95 °C (57%); (b) 61, n-BuLi, ZnCl2, to...
Scheme 24: Olefin A as an intermediate in natural product synthesis.
Scheme 25: (a) Ph3(Me)PBr, KH, benzene (66%, rac-64) or (b) AlMe3, Zn, CH2I2, THF (76%) [101]; (c) Ph3(Me)PBr, n-Bu...
Scheme 26: (a) Benzene, rt (82%) [108]; (b) K2CO3, MeOH (85%) [89]; (c) iPrOH, [Ir(COD)Cl]2, PPh3, THF, rt (81%) [114].
Scheme 27: Mechanism of the Still–Gennari modification of the HWE reaction leading to both olefin isomers.
