Asymmetric total synthesis of (+)-aphanamol I based on the transition metal catalyzed [5 + 2] cycloaddition of allenes and vinylcyclopropanes.
A concise asymmetric total synthesis of (+)-aphanamol I is described, based on the transition metal catalyzed [5 + 2] allenyl-vinylcyclopropane cycloaddition. The key cycloaddition precursor is convergently assembled from (R)-(+)-limonene and cyclopropane diester through a novel decarboxylative dehydration reaction. The metal-catalyzed [5 + 2] cycloaddition of this precursor proceeds with complete chemo, endo/exo, and diastereoselectivity in 93% yield, representing an effective general route to bicyclo[5.3.0]decane derivatives.
Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA. wenderp@leland.stanford.edu
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D000466:Alkadienes / Q000737:chemistry* / Q000378:metabolism; D052176:Azulenes; D003508:Cycloheptanes / Q000737:chemistry* / Q000378:metabolism; D053138:Cyclohexenes; D003521:Cyclopropanes / Q000737:chemistry / Q000378:metabolism; D005638:Fruit / Q000737:chemistry; D000077222:Limonene; D011083:Polycyclic Compounds / Q000138:chemical synthesis / Q000737:chemistry / Q000378:metabolism; D012717:Sesquiterpenes / Q000138:chemical synthesis* / Q000737:chemistry / Q000378:metabolism / Q000633:toxicity; D013237:Stereoisomerism; D013729:Terpenes / Q000378:metabolism
D000466:Alkadienes; D052176:Azulenes; D003508:Cycloheptanes; D053138:Cyclohexenes; D003521:Cyclopropanes; D011083:Polycyclic Compounds; D012717:Sesquiterpenes; D013729:Terpenes; C413803:aphanamol I; C025947:propadiene; C005525:azulene; C030797:cyclopropane; D000077222:Limonene