Synthesis of Chirality Controlled Optically active Ferrocenes and Their Application to Catalytic Asymmetric Synthesis

手性控制的光学活性二茂铁的合成及其在催化不对称合成中的应用

• 批准号: 18550046
• 负责人: FUKUZAWA Shin-ichi
• 金额: $ 2.64万
• 依托单位: Chuo University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2006
• 资助国家: 日本
• 起止时间: 2006 至 2007
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-18550046/
• 关键词: ferrocene; chiral ligand; phosphine ligand; Taniaphos; bridged ferrocene; allylic alkvlation; allylic amination; ortho lithiation; キラリティー; 面性不斉; サマリウム; ピナコールカップリング; 不斉合成; 錯体触媒; ルイス酸

The 1, 5-dilithiation of o-TMS blocked (dimethylamino) phenylmethylferrocene with tBuLi unexpectedly occurred and the 1, 5-dilithiated ferrocene was trapped by halogen followed by removal of the TMS group to give the 1, 5-dihaloferrocene in a reasonable yield. The 1, 5-diiodoferrocene was converted into Taniaphos ligand by the sequencial of dilithiation and trapping with Ph_2PCl. The methoxy 1, 5-diphosphane was obtained by the inversive substitution of the dimethylamino group by NaOMe and subsequent dilithiation and trapping with Ph_2PC 1. The homoannularly bridged ferrocene was prepared by the intramolecular coupling of the 1, 5-dilithioferrocene mediated by Fe(acac)_3. Its benzene ring underwent ortho-lithiation by tBuLi, and subsequent trapping with Ph_2PCl produced the corresponding aminophosphine. The aminophosphine which has the phosphinyl group on the cyclopentadienyl group was prepared by intramolecular coupling of 1, 5-dilithiated Ph-PPFA mediated by Fe(acac)_3. The new N, P-ligands were applied to the benchmark palladium complex-catalyzed allylic alkylation and amination of the 1, 3-diphenyl-2-propenyl acetate and was found to give good results (good yields with high enantioselectivities, up to 96% ee).

邻-TMS封闭的(二甲氨基)苯甲基二茂铁与tBuLi发生了意外的1，5-二锂化合反应，1，5-二锂化二茂铁被卤素捕获，然后TMS基团被脱除，以合理的产率得到1，5-二卤代二茂铁。1，5-二碘二茂铁通过二硫化和Ph_2PCl捕集的顺序转化为TaNiaphos配体。1，5-二锂硫代二茂铁在Fe(Acac)_3的作用下发生分子内偶联反应得到甲氧基-1，5-二膦，其苯环被tBuLi邻位锂化合，然后用Ph_2PCl捕获生成相应的氨基膦。以Fe(Acac)_3为催化剂，通过1，5-二锂基膦对苯二甲酸的分子内偶联反应合成了环戊二烯基上含膦基团的氨基膦，并将其应用于基准钯配合物催化的1，3-二苯基-2-丙烯基乙酸酯的烯丙烷基化和胺化反应，得到了较好的结果(产率高，对映选择性高，ee高达96%ee)。

项目成果

クリックケミストリーを用いたキラルフェロセニルポスフィン配位子の合成と不斉反応への応用

利用点击化学合成手性二茂铁基膦配体及其在不对称反应中的应用

• 发表时间: 2007
• 作者: 保坂 光輝;菊地 哲;福澤 信一
• 通讯作者: 福澤 信一

Unexpected 1,5-Dilithiation of Chiral o-TMS Blocked (Dimethylamino)phenylmethylferrocene; An Alternative Approach to Chiral Ferrocenyl 1,5-Diphosphanes

手性 o-TMS 封闭的（二甲氨基）苯基甲基二茂铁意外发生 1,5-二锂化；

• 发表时间: 2007
• 期刊: The Journal of Organic Chemistry 72
• 作者: Shin-ichi Fukuzawa;Daisuke Tanihara;Satoshi Kikuchi
• 通讯作者: Satoshi Kikuchi

Prepation of New Chiral Ferrocenyl Phosphine and Amine Ligands and Their Application to Asymmetric Synthesis

新型手性二茂铁基膦和胺配体的制备及其在不对称合成中的应用

• 发表时间: 2007
• 作者: Shin-ichi;Fukuzawa
• 通讯作者: Fukuzawa

Preparation of Chiral Homoannularly Bridged N,P-Ferroceriyl Ligands by Intramolecular Coupling of 1,5-Dilithioferrocenes and Their Application in Asymmetric Allylic Substitution Reactions

1,5-二锂硫代二茂铁分子内偶联制备手性同环桥联N,P-二茂铁基配体及其在不对称烯丙基取代反应中的应用

• 发表时间: 2007
• 期刊: European Journal of Organic Chemistry
• 影响因子: 2.8
• 作者: Shin-ichi Fukuzawa;Masahisa Yamamoto;Mitsuteru Hosaka;Satoshi Kikuchi
• 通讯作者: Satoshi Kikuchi

ClickFerrqphos:New Chiral Ferrocenyl Phosphine Liganaa Synthesized by Click Chemistry and the Use of Their Metal Complexes as Catalysts for Asymmetric Hydrogenation and Allylic Substitution

ClickFerrqphos：点击化学合成的新型手性二茂铁基膦 Liganaa 及其金属配合物作为不对称氢化和烯丙基取代催化剂的用途

• 发表时间: 2007
• 期刊: Organic Letters 9
• 作者: Shin-ichi Fukuzawa;Hiroshi Oki;Mitsuteru Hosaka;Jun Sugasawa;Satoshi Kikuchi
• 通讯作者: Satoshi Kikuchi