Search for New Synthetic Reactions using Acylzirconocene Complex as an "Unmasked" Acyl Anion

使用酰基二茂锆络合物作为“未掩蔽的”酰基阴离子寻找新的合成反应

• 批准号: 10672000
• 负责人: HANZAWA Yuji
• 金额: $ 1.73万
• 依托单位: Tokyo University of Pharmacy and Life Science
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10672000/
• 关键词: Early transition metal; Acylzirconocene complex; Catalytic reaction; Coupling reaction; Regioselective reaction; Asymmetric synthesis; アシルアニオン; アシルジルコノセン; 銅触媒; シアノクプラート; ケトンα,β-ジアニオン; 求核反応; パラジウム触媒; α,B-不飽和ケトン; 位置選択性; エナンチオ選択性

In our ongoing research project on new synthetic reactions using acylzirconocene complex, we have exploited enormous possibilities of acylzirconocene complex for organic synthesis. During the past term of the project we established several quite new synthetic reactions in which acylzirconocene chloride reacted with aldehyde in the presence of a stoichiometric amount of Lewis acid to give a-ketol derivatives. It is the first example that the acylzirconocene chloride reacts as an "unmasked" acyl anion. We also found a Pd-catalyzed reaction of acylzirconocene chloride with organic halides to give ketone derivatives. Moreover, in the Pd-catalyzed conditions, acylzirconocene complex adds to α, β-unsaturated ketones, regioselectively. In the 1, 2-selective addition conditions, an enantioselective addition of the "unmasked" acyl anion was achieved for the first time by the use of chiral phosphine ligand. Although the asymmetric induction (66% ee) in the present reaction is not satisfactorily high yet, we are currently continuing the research to find more effective chiral ligand for zirconium metal complex.

在我们正在进行的使用酰基锆茂络合物的新合成反应的研究项目中，我们已经开发了酰基锆茂络合物用于有机合成的巨大可能性。在项目的前期工作中，我们建立了几个新的合成反应，即在化学计量的刘易斯酸存在下，酰基二茂锆氯化物与醛反应生成α-酮醇衍生物。这是第一个例子，酰基氯化锆茂作为一个“未掩蔽”的酰基阴离子反应。我们还发现了钯催化的酰基二茂锆氯化物与有机卤化物的反应，得到酮衍生物。此外，在钯催化条件下，酰基锆茂配合物对α，β-不饱和酮具有区域选择性加成反应。在1，2-选择性加成条件下，首次利用手性膦配体实现了“未掩蔽”酰基阴离子的对映选择性加成。虽然在本反应中的不对称诱导（66%ee）还不是令人满意的高，我们目前正在继续研究，以找到更有效的锆金属配合物的手性配体。

项目成果

HARADA, S.: "Acylzirconocene Chloriclle as am "Oninasked" Acyl Anion"Angew, Chem. Int. Ed. 37. 1696-1698 (1998)

HARADA, S.：“Acylzirconocene Chloriclle as am“Oninasked”酰基阴离子”Angew，Chem。

Hanzawa Y.: "A Cp2TiCl2-AlCl3 (1 : 4) Reagent System : An Efficient Reagent for Generation of Allylic Titanocene Derivatives from Vinyl Halides, Vinyl Esters and Carboxylic Esters"Tetrahedron. 54. 11387-11398 (1998)

Hanzawa Y.：“Cp2TiCl2-AlCl3 (1:4) 试剂系统：用于从乙烯基卤化物、乙烯基酯和羧酸酯生成烯丙基二茂钛衍生物的有效试剂”四面体。

Hanzawa Y.: "Palladium-Catalyzed Reactions of Acylzirconocene Chloride with Organic Halides"Tetrahedron Lett.. 39. 6249-6252 (1998)

Hanzawa Y.：“酰基二茂锆氯化物与有机卤化物的钯催化反应”Tetrahedron Lett.. 39. 6249-6252 (1998)

Hanzawa Y.: "Palladium-Catalyzed Acylation Reactions of α, β-Unsaturated Ketones with Acylzirconocene Chloride : Remarkable Control of 1, 2- and 1, 4-Selectivity by the Catalyst"Tetrahedron Lett.. 39. 8141-8144 (1998)

Hanzawa Y.：“钯催化的 α, β-不饱和酮与酰基锆茂氯化物的酰化反应：催化剂对 1, 2- 和 1, 4-选择性的显着控制”Tetrahedron Lett.. 39. 8141-8144 (1998)

Hanzawa Y.: "Acylzirconocene Chloride as an "Unmasked" Acyl Anion : Enantioselective 1, 2-Addition to α,β-Unsaturated Ketone Derivatives"Angew.Chem.Int.Ed.. 38. 2395-2398 (1999)

Hanzawa Y.：“酰基锆茂氯化物作为“未掩蔽的”酰基阴离子：对 α,β-不饱和酮衍生物的对映选择性 1, 2-加成”Angew.Chem.Int.Ed.. 38. 2395-2398 (1999)