呋喃
化学
废止
环加成
烯酮
全合成
亚砜
除氧
环己酮
艾伦
对映选择合成
酮
烯酮
戒指(化学)
有机合成
立体化学
二萜
天然产物
有机化学
催化作用
作者
Joseph Benford‐Ward,Sanaz Ahmadipour,Aliya Sembayeva,Louise Male,Richard S. Grainger
标识
DOI:10.1002/chem.202202429
摘要
The dolabellane-type diterpene dictyoxetane represents a significant challenge to synthetic organic chemistry. Methodology directed towards the total synthesis of naturally occurring (+)-dictyoxetane is reported. Catalytic asymmetric synthesis of the trans-hydrindane ring system is achieved through chemoselective deoxygenation of the Hajos-Parrish ketone. An alternative to the Garst-Spencer furan annulation is developed for the synthesis of a 2,5-dimethyl, tetrasubstituted furan, employing a tandem 5-exo-dig alcohol to alkyne cyclisation/aromatisation reaction as a key step. The (4+3) cycloaddition reaction of an oxyallyl cation with a tetrasubstituted furan is established on a cyclohexanone-derived model system, and a range of related (4+3) cycloadditions investigated on a homochiral, trans-hydrindane-fused furan, where regio- and diastereoselectivity is required for the natural product synthesis. In an alternative (4+2) Diels-Alder approach, a C2 -symmetric vinyl sulfoxide-based chiral ketene equivalent is used to prepare oxanorbornenes with the same oxygen bridge stereochemistry found in the 2,7-dioxatricyclo[4.2.1.03,8 ]nonane ring system of the natural product.
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