The synthesis and the odor tonalities of racemic 5-demethyl-α-ionone are described. This synthetic ionone derivative did not show the typical floral-woody violet smell of α-ionone, definitely proving the importance of a suitably sized and spatially oriented alkyl substituent at C(5) for stimulating olfactory receptors of ionones.
TiemannF, KrügerP. (1893) Ueber Veilchenaroma. Berichte der Deutschen Chemischen. Gesellshaft, 26, 2675–2708.
2.
BauerK, GarbeD, SurburgH. (2001) Common Fragrance and Flavor Materials, 4th edn., Wiley-VCH, Weinheim, Germany,
3.
OhloffG., PickenhagenW, KraftP. (2012) Scent and Chemistry – The Molecular World of Odors. Wiley-VCH, Weinheim, Germany.
4.
ChapuisC, BrauchliR. (1993) Preparation of optically active flowery and woody-like odorant ketones via Corey-Chaykovsky oxiranylation: Irones and analogues. Helvetica Chimica Acta, 76, 2070–2088.
SestanjK. (1962) Synthesis of an acyclic analog of ionone. Croatica Chemica Acta, 34, 211–217.
8.
StollM, ScherrerW. (1940) Produits à odeur de violette VIII. Synthèse du 1,1,6-triméthyl-3-(butène-31-ylone-33)-cycloheptène. Helvetica Chimica Acta, 23, 941–948;
9.
RouvéA, StollM. (1947) Produits à odeur de violette. Synthèse de la 5-méthyl-ionone. Helvetica Chimica Acta, 30, 2216–2220.
10.
KraftP. (1999) Design and synthesis of violet odorants with bicyclo[6.4.0]dodecene and bicyclo[5.4.0]undecene skeletons. Synthesis, 695–703;
11.
KraftP, BajgrowiczJA, DenisC, FráterG. (2000) Odds and trends: Recent developments in the chemistry of odorants. Angewandte. Chemie International Edition, 39, 2980–3010.
12.
SellCS. (2006) On the unpredictability of odor. Angewandte. Chemie International Edition, 45, 6254–6261.
BuckLB, AxelR. (1991) A novel multigene family may encode odorant receptors: A molecular basis for odor recognition. Cell, 65, 175–187;
15.
AxelR. (2005) Scents and sensibility: A molecular logic of olfactory perception (Nobel lecture). Angewandte. Chemie International Edition, 44, 6110–6127;
16.
BuckLB. (2005) Unraveling the Sense of Smell (Nobel Lecture). Angewandte Chemie International Edition, 44, 6128–6140;
17.
ZozulyaS, EcheverriF, NguyenT. (2001) The human olfactory receptor repertoire. Advances in Genome Biology, 2, research 0018.1–0018.12;
18.
KrautwurstD. (2008) Human Olfactory Receptor Families and Their Odorants. Chemistry & Biodiversity, 5, 842–852.
19.
SellC. (Ed). (2006) The chemistry of fragrances. The Royal Society of Chemistry, Cambridge, UK.
20.
Other factors such as ligand volatility, solubility, and lipophilicity, as well as intrinsic entropic factors, are also important in determining the olfactory properties of compounds. They, however, should not vary significantly among structurally similar molecules.
21.
LupariaM, BoschettiP, PiccininiF, PortaA, ZanoniG, VidariG. (2008) Enantioselective synthesis and olfactory evaluation of 13-alkyl-substituted α-ionones. Chemistry & Biodiversity, 5, 1045–1057;
22.
LupariaM, LegnaniL, PortaA, ZanoniG, TomaL, VidariG. (2009) Enantioselective synthesis and olfactory evaluation of bicyclic α- and γ-ionone derivatives: The 3D arrangement of key molecular features relevant to the violet ddor of ionones. Journal of Organic Chemistry, 74, 7100–7110;
23.
BugoniS, MerliniV, PortaA, ZanoniG, VidariG. (2014) A general and concise enantioselective divergent approach to 13-alkyl-substituted ionones. Chemistry & Biodiversity, 11, 1540–1553.
24.
SerraS, FugantiC, BrennaE. (2006) Synthesis, olfactory evaluation, and determination of the absolute configuration of the 3,4-didehydroionone stereoisomers. Helvetica Chimica Acta, 89, 1110–1122.
25.
LegnaniL, LupariaM, ZanoniG, TomaL, VidariG. (2008) A full conformational characterization of natural ionones and irones, as well as 13-alkyl-substituted α-ionones. European Journal of Organic Chemistry, 4755–4762.
26.
JitkowON, BogertMT. (1941) The relationship between structure and odor in the case of certain derivatives of 2,2,4-trimethyl-Δ3-cyclohexene aldehyde. Journal of the American Chemical Society, 63, 1979–1984.
27.
ShapiroRH. (1976) Alkenes from tosylhydrazones. Organic Reaction, 23, 405–507.
28.
SumFW, WeilerL. (1979) Stereoselective synthesis of β-substituted α,β-unsaturated esters by dialkylcuprate coupling to the enol phosphate of β-keto esters. Canadian Journal of Chemistry, 57, 1431–1441.
29.
YamamotoY, TakedaY, AkibaK. (1989) Intramolecular cyclization of o-silylbenzyl alcohols with elimination of hydrocarbon via hypervalent silicon intermediate: effect of structure on the selectivity for elimination. Tetrahedron Letters, 30, 725–728.
30.
BartonDHR, O'BrienRE, SternhellS. (1962) A new reaction of hydrazones. Journal of the Chemical Society Part I, 470–476.
31.
OzanneA, PouyseguL, DepernetD, FrancoisB, QuideauS. (2003) A stabilized formulation of IBX (SIBX) for safe oxidation reactions including a new oxidative demethylation of phenolic methyl aryl ethers. Organic Letters, 5, 2903–2906.
32.
FugantiC, SerraS, ZenoniA. (2000) Synthesis and olfactory evaluation of (+)- and (-)-γ-ionone. Helvetica Chimica Acta, 83, 2761–2768.
