13456-36-5Relevant academic research and scientific papers
Synthesis of (+)-sclareolide based on a cyclic enol ether ring contraction induced by peroxy acids
Castro, Juan M.,Salido, Sofía,Sánchez, Adolfo,Altarejos, Joaquín
, p. 2747 - 2750 (2010)
(+)-Sclareolide has been synthesised from (+)-sclareol oxide in one step in high yield, by treatment with peroxy acids under very mild conditions. The reaction pathway does not follow the usual oxidative cleavage of the double bond of (+)-sclareol oxide, but the key intermediate is a five-membered ring hemiketal. The direct conversion of a six-membered cyclic enol ether into a γ-lactone is described for the first time.
Making Fe(BPBP)-catalyzed C-H and CC oxidations more affordable
Yazerski, Vital A.,Spannring, Peter,Gatineau, David,Woerde, Charlotte H.M.,Wieclawska, Sara M.,Lutz, Martin,Kleijn, Henk,Klein Gebbink, Robertus J.M.
supporting information, p. 2062 - 2070 (2014/03/21)
The limited availability of catalytic reaction components may represent a major hurdle for the practical application of many catalytic procedures in organic synthesis. In this work, we demonstrate that the mixture of isomeric iron complexes [Fe(OTf)2(mix-BPBP)] (mix-1), composed of Λ-α-[Fe(OTf)2(S,S-BPBP)] (S,S-1), Δ-α- [Fe(OTf)2(R,R-BPBP)] (R,R-1) and Δ/Λ-β-[Fe(OTf) 2(R,S-BPBP)] (R,S-1), is a practical catalyst for the preparative oxidation of various aliphatic compounds including model hydrocarbons and optically pure natural products using hydrogen peroxide as an oxidant. Among the species present in mix-1, S,S-1 and R,R-1 are catalytically active, act independently and represent ca. 75% of mix-1. The remaining 25% of mix-1 is represented by mesomeric R,S-1 which nominally plays a spectator role in both C-H and C=C bond oxidation reactions. Overall, this mixture of iron complexes displays the same catalytic profile as its enantiopure components that have been previously used separately in sp3 C-H oxidations. In contrast to them, mix-1 is readily available on a multi-gram scale via two high yielding steps from crude dl/meso-2,2′-bipyrrolidine. Next to its use in C-H oxidation, mix-1 is active in chemospecific epoxidation reactions, which has allowed us to develop a practical catalytic protocol for the synthesis of epoxides.
PROCESS FOR THE CYCLODEHYDRATION OF DIOLS AND USE THEREOF FOR THE MANUFACTURING OF AMBRAFURAN AND OTHER CYCLOETHER DERIVATIVES
-
, (2013/03/26)
The present invention relates to a process for manufacturing tetrahydrofuran, tetrahydropyran and, more generally, cycloether derivatives through the cyclodehydration of 1,4- or 1,5- diols. More specifically, the process of the invention involves (i) the stereoselective cyclodehydration in water of 1,4- or 1,5- diols comprising at least one chiral tertiary alcohol functional group with retention of the initial chirality, and/or (ii) the cyclodehydration in water of 1,4- or 1,5- diols, said diols being non-miscible with and/or non-soluble in water, into corresponding cycloether derivatives, by bringing the reaction mixture to high temperature water (HTW) conditions and/or by mixing the aqueous reaction mixture with a solid catalyst, such as for example a smectite clay. The present invention further relates to the use of the process of the invention for manufacturing ambrafuran, especially (-)-ambrafuran and other cycloether derivatives.
Synthesis of nor-ambreinolide from (+)-cis-abienol
Barrero, Alejandro F.,Sanchez, Juan F.,Alvarez-Manzaneda, Enrique J.,Altarejos, Joaquin,Munoz, Manuel,Haidour, Ali
, p. 6653 - 6662 (2007/10/02)
The synthesis of nor-ambreinolide (2) from cis-abienol (1) was carried out by direct treatment with OsO4-NaIO4 or RuO4-NaIO4. The oxymercuriation-demercuriation of 1 led to a mixture of 8,12-epoxylabdanes (5-17) which was also converted into nor-ambreinolide by treatment with RuO4-NaIO4. The formation pathways of such epoxy derivatives are discussed.
