“…Toward this end, we needed to prepare the allyl−vinyl ether 13 , required for the Claisen rearrangement, and to our dismay, treatment of allylic alcohol 12 with ethylvinylether and Hg(OAc) 2 in the presence of NaOAc gave 13 in poor yield. Alternatively, when the Johnson−Claisen rearrangement and the Ireland−Claisen rearrangement were attempted on the alcohol 12 , yet again, these reactions did not lead to the required products. 2 Synthesis of Aldehyde 15 …”
An enantioselective route for the synthesis of oxatetracyclic core of platensimycin is reported for the first time using a 5-exo-trig cyclization followed by intramolecular etherification as key reactions. The requisite dienynone for the radical cyclization is synthesized in eight steps from the Wieland-Miescher ketone employing a Claisen rearrangement.
“…Toward this end, we needed to prepare the allyl−vinyl ether 13 , required for the Claisen rearrangement, and to our dismay, treatment of allylic alcohol 12 with ethylvinylether and Hg(OAc) 2 in the presence of NaOAc gave 13 in poor yield. Alternatively, when the Johnson−Claisen rearrangement and the Ireland−Claisen rearrangement were attempted on the alcohol 12 , yet again, these reactions did not lead to the required products. 2 Synthesis of Aldehyde 15 …”
An enantioselective route for the synthesis of oxatetracyclic core of platensimycin is reported for the first time using a 5-exo-trig cyclization followed by intramolecular etherification as key reactions. The requisite dienynone for the radical cyclization is synthesized in eight steps from the Wieland-Miescher ketone employing a Claisen rearrangement.
“…With both enantiomers of azedaralide in hand, these could now be applied to either synthesis of (+)- or (−)-cipadonoid B ( 4 ). The known, but rarely applied, ketal–Claisen rearrangement − used in the synthesis of racemic (±)-cipadonoid B ( 4 ) (Scheme ), however, was poorly understood in terms of stereochemical outcome. In brief, when this reaction was performed in the racemic series it produced undesired diastereoisomers (i.e., 13 and 15 ) of the natural product cipadonoid B ( 4 ).…”
The enantioselective total synthesis of the limonoids khayasin, proceranolide and mexicanolide was achieved via a convergent strategy utilizing a tactic aimed at incorporating natural products as advanced intermediates. This extended biomimetically inspired approach additionally achieved the enantioselective total synthesis of the intermediates azedaralide and cipadonoid B.
“…Homoallylic ketones (γ,δ-unsaturated ketones) are useful intermediates for the synthesis of various compounds, including cyclic alkanes, 1 natural products, 2 and drugs. 3,4 They are generally synthesised by 1,4-conjugate addition of vinyl organometallic reagents 5 to α,β-unsaturated ketones and nucleophilic substitutions of ketones and allylic compounds ( e.g. , allylic alcohol, allylic halide, and allyl acetate) (Fig.…”
Homoallylic ketones are useful intermediates for the synthesis of various compounds, such as drugs and natural products. However, the currently available fabrication methods for homoallylic ketones are environmentally unfriendly and...
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