Organometallic derivatives of natural products: dicobalt hexacarbonyl complexes of geranyl-alkynes
Organometallic derivatives of natural products: dicobalt hexacarbonyl complexes of geranyl-alkynes
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天然产物有机金属衍生物：香叶基炔烃二钴六羰基配合物
DOI：
10.1039/c6nj00622a
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发表时间：
2016
影响因子：
3.3
通讯作者：
M. McGlinchey
中科院分区：
文献类型：
--
作者：
Angela Moore;J. Ostermann;Y. Ortin;M. McGlinchey
甲基香叶醚与二铁非羰基处理导致氢迁移，以低收率生成以前未知的E和z1 -甲氧基-3,7-二甲基-1,6-辛二烯。丙炔醇氧钠和香叶基溴化产丙炔香叶醚，13；随后与八羰基二钴和二苯基膦甲烷反应得到相应的炔- co2 (CO)4（dppm）四面体簇，16。香叶酮与苯乙基锂，再与Co2(CO)8反应，生成（1-苯基-3,7,11-三甲基十二-6,10-二烯-1-炔-3-醇）Co2(CO) 6,19。羰基三钴壬羰基簇RC(O)CCo3(CO)9，其中R =香叶基23，或法尼基25，可以通过适当的醇与三氯乙酰氯和Co2(CO)8反应，或与金属稳定的酰基离子[Co3(CO)9CCO]+， 24反应，以非常高的收率制备。讨论了这些（η - 2-炔）二钴配合物在Pauson-Khand或Nicholas环化中的潜在用途。
Treatment of methyl geranyl ether with diiron nonacarbonyl leads to hydrogen migration to form previously unknown E and Z 1-methoxy-3,7-dimethyl-1,6-octadiene in low yield. Sodium propargyl alkoxide and geranyl bromide yield propargyl geranyl ether, 13; subsequent reaction with dicobalt octacarbonyl and then bis(diphenylphosphino)methane furnishes the corresponding alkyne–Co2(CO)4(dppm) tetrahedral cluster, 16. Reaction of geranylacetone with phenylethynyl-lithium, and then with Co2(CO)8, forms (1-phenyl-3,7,11-trimethyldodeca-6,10-dien-1-yn-3-ol)Co2(CO)6, 19. The carbynyltricobaltnonacarbonyl clusters RC(O)CCo3(CO)9, where R = geranyl, 23, or farnesyl, 25, are preparable in very good yield either by reaction of the appropriate alcohol with trichloroacetyl chloride and then Co2(CO)8, or by reaction with the metal-stabilized acylium ion [Co3(CO)9CCO]+, 24. Potential use of these (η2-alkyne)dicobalt complexes in Pauson–Khand or Nicholas cyclizations is discussed.