berkeleyone B | 1334495-42-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: berkeleyone B
• 英文别名: methyl (1R,2S,11S,12S,14R,16S)-16-hydroxy-2,6,6,11,14,16-hexamethyl-18-methylidene-8,15,17-trioxo-7-oxatetracyclo[12.3.1.02,12.05,11]octadec-4-ene-1-carboxylate
• CAS: 1334495-42-9
• 化学式: C₂₆H₃₄O₇
• 分子量: 458.552
• InChiKey: IWYHWTWGKBGNTO-GSISZECUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  33
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  107
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  berkeleyone B 在 α-ketoglutarate-dependent dioxygenase PrhA 作用下， 以3.06 mg的产率得到berkeleydione
  参考文献：
  名称：

  Discovery of Key Dioxygenases that Diverged the Paraherquonin and Acetoxydehydroaustin Pathways in Penicillium brasilianum

  摘要：

  Paraherquonin (1), a fungal meroterpenoid produced by Penicillium brasilianum NBRC 6234, possesses a unique, highly congested hexacyclic molecular architecture. Here we identified the biosynthetic gene cluster of 1 (the prh cluster) and elucidated the pathway up to berkeleydione (2), which serves as the key intermediate for the biosynthesis of I as well as many other meroterpenoids. Interestingly, the nonheme iron and a-ketoglutarate-dependent dioxygenase PrhA constructs the cycloheptadiene moiety to afford 2 from preaustinoid A1 (6), probably via the homoallyl-homoallyl radical rearrangement. Additionally, another fungal strain, P. brasilianum MG11, which produces acetoxydehydroaustin instead of 1, was found to have a gene cluster nearly identical to the prh cluster. The dioxygenase encoded by the cluster shares 92% sequence identity with PrhA, and also accepts 6 but produces preaustinoid A3 (17) with a spiro-lactone system, generating a diverging point for the two different meroterpenoid pathways in the same species.

  DOI：

  10.1021/jacs.6b08424
• 作为产物：
  描述：

  protoaustinoid A 在 α-ketoglutarate-dependent dioxygenase PrhA 、 flavin-dependent monooxygenase PrhJ 、 flavin-dependent monooxygenase PrhK 、 short-chain dehydrogenase/reductase PrhI 作用下， 生成 berkeleyone B
  参考文献：
  名称：

  Discovery of Key Dioxygenases that Diverged the Paraherquonin and Acetoxydehydroaustin Pathways in Penicillium brasilianum

  摘要：

  Paraherquonin (1), a fungal meroterpenoid produced by Penicillium brasilianum NBRC 6234, possesses a unique, highly congested hexacyclic molecular architecture. Here we identified the biosynthetic gene cluster of 1 (the prh cluster) and elucidated the pathway up to berkeleydione (2), which serves as the key intermediate for the biosynthesis of I as well as many other meroterpenoids. Interestingly, the nonheme iron and a-ketoglutarate-dependent dioxygenase PrhA constructs the cycloheptadiene moiety to afford 2 from preaustinoid A1 (6), probably via the homoallyl-homoallyl radical rearrangement. Additionally, another fungal strain, P. brasilianum MG11, which produces acetoxydehydroaustin instead of 1, was found to have a gene cluster nearly identical to the prh cluster. The dioxygenase encoded by the cluster shares 92% sequence identity with PrhA, and also accepts 6 but produces preaustinoid A3 (17) with a spiro-lactone system, generating a diverging point for the two different meroterpenoid pathways in the same species.

  DOI：

  10.1021/jacs.6b08424

文献信息

• Discovery of Key Dioxygenases that Diverged the Paraherquonin and Acetoxydehydroaustin Pathways in <i>Penicillium brasilianum</i>
  作者：Yudai Matsuda、Taiki Iwabuchi、Takayuki Fujimoto、Takayoshi Awakawa、Yu Nakashima、Takahiro Mori、Huiping Zhang、Fumiaki Hayashi、Ikuro Abe

  DOI：10.1021/jacs.6b08424

  日期：2016.9.28

  Paraherquonin (1), a fungal meroterpenoid produced by Penicillium brasilianum NBRC 6234, possesses a unique, highly congested hexacyclic molecular architecture. Here we identified the biosynthetic gene cluster of 1 (the prh cluster) and elucidated the pathway up to berkeleydione (2), which serves as the key intermediate for the biosynthesis of I as well as many other meroterpenoids. Interestingly, the nonheme iron and a-ketoglutarate-dependent dioxygenase PrhA constructs the cycloheptadiene moiety to afford 2 from preaustinoid A1 (6), probably via the homoallyl-homoallyl radical rearrangement. Additionally, another fungal strain, P. brasilianum MG11, which produces acetoxydehydroaustin instead of 1, was found to have a gene cluster nearly identical to the prh cluster. The dioxygenase encoded by the cluster shares 92% sequence identity with PrhA, and also accepts 6 but produces preaustinoid A3 (17) with a spiro-lactone system, generating a diverging point for the two different meroterpenoid pathways in the same species.