A practical deca-gram scale ring expansion of (R)-(-)-carvone to (R)-(+)-3-methyl-6-isopropenyl-cyclohept-3-enone-1
A practical deca-gram scale ring expansion of (R)-(-)-carvone to (R)-(+)-3-methyl-6-isopropenyl-cyclohept-3-enone-1
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DOI：
10.1039/c5ob00525f
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发表时间：
2015-01-01
影响因子：
3.2
通讯作者：
Brocksom, Timothy J.
中科院分区：
文献类型：
--
作者：
Alves, Leandro de C.;Desidera, Andre L.;Brocksom, Timothy J.
通过高度化学选择性和区域选择性的Tiffeneau-Demjanov反应，合成了一种萜类化合物中间体（R）-（+）-3-甲基-6-异丙烯基-环庚-3-烯酮-1。从容易获得的（R）-（-）-香芹酮开始，这种稳健的序列可在十克规模上获得，并使用流动化学进行初始环氧化反应。用X-射线衍射和化学关联法确定了（R）-（-）-香芹酮羰基上两个亲核试剂的加成立体化学。
A route to enantiopure (R)-(+)-3-methyl-6-isopropenyl-cyclohept-3-enone-1, an intermediate for terpenoids, has been developed and includes a highly chemo- and regioselective Tiffeneau-Demjanov reaction. Starting from readily available (R)-(-)-carvone, this robust sequence is available on a deca-gram scale and uses flow chemistry for the initial epoxidation reaction. The stereochemistry of the addition of two nucleophiles to the carbonyl group of (R)-(-)-carvone has been determined by X-ray diffraction studies and chemical correlation.