3-Methylene-3a,4,5,7a-tetrahydro-3H-benzofuran-2-one | 343270-98-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并呋喃
• 英文名称: 3-Methylene-3a,4,5,7a-tetrahydro-3H-benzofuran-2-one
• 英文别名: 3-Methylidene-3a,4,5,7a-tetrahydro-1-benzofuran-2-one
• CAS: 343270-98-4
• 化学式: C₉H₁₀O₂
• 分子量: 150.177
• InChiKey: OWXXTXZKQXMYEX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-(-)- α-甲基苄胺 、 3-Methylene-3a,4,5,7a-tetrahydro-3H-benzofuran-2-one 在 正丁基锂 作用下， 生成 2-((1S,2S)-2-Hydroxy-cyclohex-3-enyl)-N-((S)-1-phenyl-ethyl)-acrylamide
  参考文献：
  名称：

  Synthesis of a novel type of chiral phosphinocarboxylic acids. The phosphine-palladium complexes catalyzed asymmetric allylic alkylation

  摘要：

  A novel type of chiral cycloalkylphosphines bearing the carboxy group at the beta-position were developed, and used for palladium catalyzed asymmetric alkylation of allylic substrates such as 2-cyclohexenylacetate and 1,3-disubstituted-propenyl acetates (R1CH = CHCH(OAc)R2: R1 = R2 = Ph; R1 = Ph, R2 = (CH2)4OAc; R1 = Ph, R2 = (CH2)6OAc; R1 = Ph, R2 = (CH2)10OAc). Reaction of the propenyl acetates with soft carbon nucleophiles such as triethyl sodiophosphonoacetate and sodiomalonic acid esters in the presence of a palladium catalyst prepared in situ from Pd(OAc)2 and chiral (2-diphenylphosphino)cycloalkanecarboxylic acids (7a,b) gave high yields of alkylation products (PhCH = CHCH(X)Ph: > 77 %ee for X = CH(CO2Et)P(O)(OEt)2 and > 72 %ee for X = CH(CO2Me)2). The alkylation products 15 and 28a-c were converted into optically active alpha-methylene-gamma-lactone and alpha-methylene macrolide derivatives. The high stereoselectivity demonstrated by the chiral phosphinocarboxylic acid-palladium catalyzed allylic alkylation suggested to be caused by an electronic repulsion between the carboxy group on the ligand and the incoming soft carbon nucleophile, which directs the nucleophilic attack on one of the pi-allyl carbons.

  DOI：

  10.1016/s0957-4166(00)86121-2
• 作为产物：
  描述：

  3-diethoxyphosphoryl-3a,4,5,7a-tetrahydro-3H-1-benzofuran-2-one 生成 3-Methylene-3a,4,5,7a-tetrahydro-3H-benzofuran-2-one
  参考文献：
  名称：

  MINAMI, TORU;HIRAKAWA, KAZUNARI;KOYANAG, SHINICHIRO;NAKAMURA, SEIGO;YAMAG+, J. CHEM. SOC. PERKIN TRANS. PT. 1,(1990) N, C. 2383-2390

  摘要：

  DOI：

文献信息

• RAUCHER S.; HWANG KI-JUN; MACDONALD J. E., TETRAHEDRON LETT., 1979, NO 33, 3057-3060
  作者：RAUCHER S.、 HWANG KI-JUN、 MACDONALD J. E.

  DOI：——

  日期：——
• MINAMI, TORU;HIRAKAWA, KAZUNARI;KOYANAG, SHINICHIRO;NAKAMURA, SEIGO;YAMAG+, J. CHEM. SOC. PERKIN TRANS. PT. 1,(1990) N, C. 2383-2390
  作者：MINAMI, TORU、HIRAKAWA, KAZUNARI、KOYANAG, SHINICHIRO、NAKAMURA, SEIGO、YAMAG+

  DOI：——

  日期：——
• YU, LIN-CHEN;HELQUIST, P., SYNTH. COMMUN., 1981, 11, N 7, 591-597
  作者：YU, LIN-CHEN、HELQUIST, P.

  DOI：——

  日期：——
• YU, LIN-CHEN;HELQUIST, P., J. ORG. CHEM., 1981, 46, N 22, 4536-4541
  作者：YU, LIN-CHEN、HELQUIST, P.

  DOI：——

  日期：——
• Synthesis of a novel type of chiral phosphinocarboxylic acids. The phosphine-palladium complexes catalyzed asymmetric allylic alkylation
  作者：Yoshiharu Okada、Toru Minami、Yasuo Umezu、Shinji Nishikawa、Ryoji Mori、Yutaka Nakayama

  DOI：10.1016/s0957-4166(00)86121-2

  日期：1991.1

  A novel type of chiral cycloalkylphosphines bearing the carboxy group at the beta-position were developed, and used for palladium catalyzed asymmetric alkylation of allylic substrates such as 2-cyclohexenylacetate and 1,3-disubstituted-propenyl acetates (R1CH = CHCH(OAc)R2: R1 = R2 = Ph; R1 = Ph, R2 = (CH2)4OAc; R1 = Ph, R2 = (CH2)6OAc; R1 = Ph, R2 = (CH2)10OAc). Reaction of the propenyl acetates with soft carbon nucleophiles such as triethyl sodiophosphonoacetate and sodiomalonic acid esters in the presence of a palladium catalyst prepared in situ from Pd(OAc)2 and chiral (2-diphenylphosphino)cycloalkanecarboxylic acids (7a,b) gave high yields of alkylation products (PhCH = CHCH(X)Ph: > 77 %ee for X = CH(CO2Et)P(O)(OEt)2 and > 72 %ee for X = CH(CO2Me)2). The alkylation products 15 and 28a-c were converted into optically active alpha-methylene-gamma-lactone and alpha-methylene macrolide derivatives. The high stereoselectivity demonstrated by the chiral phosphinocarboxylic acid-palladium catalyzed allylic alkylation suggested to be caused by an electronic repulsion between the carboxy group on the ligand and the incoming soft carbon nucleophile, which directs the nucleophilic attack on one of the pi-allyl carbons.