Weinreb酰胺是合成一些结构有意义或有生物活性的手性化合物的重要中间体,它可与有机金属试剂反应生成酮,又可被二异丁基铝氢(DIBAL-H),氢化铝锂(Li Al H4)等还原成醛,现已被普遍应用于全合成化学、药物化学以及生物有机化学等领域。因...Weinreb酰胺是合成一些结构有意义或有生物活性的手性化合物的重要中间体,它可与有机金属试剂反应生成酮,又可被二异丁基铝氢(DIBAL-H),氢化铝锂(Li Al H4)等还原成醛,现已被普遍应用于全合成化学、药物化学以及生物有机化学等领域。因此,研究Weinreb酰胺的合成具有重大意义。本文综述了以羧酸、羧酸衍生物等为原料制备Weinreb酰胺的方法并对制备Weinreb酰胺的方法进行了展望。展开更多
Peptidyl epoxyketones were potential antitumor agents due to their 20S proteasome inhibitory activities. Based on their structures and special inhibitory mechanism, a series of compounds were designed by linking the e...Peptidyl epoxyketones were potential antitumor agents due to their 20S proteasome inhibitory activities. Based on their structures and special inhibitory mechanism, a series of compounds were designed by linking the epoxyketone moiety (the Cterminal pharmacophore) and the peptide backbones. To make these compounds, we used a novel method to prepare the terminal α,β-unsaturated ketone, the crucial intermediate, from Weinreb amide with satisfactory yield (62%-65%).展开更多
An unexpected decarboxamidation of a-arylsulfonyl Weinreb amides as a side reaction under the standardacylating conditions was found in Weirtreb amides chemistry. The control experiments for mechanism study disclosedt...An unexpected decarboxamidation of a-arylsulfonyl Weinreb amides as a side reaction under the standardacylating conditions was found in Weirtreb amides chemistry. The control experiments for mechanism study disclosedthat a-sulfo group was necessary, and a-quaternary carbon was the key factor for the reaction. Meanwhile, an effi-cient method was established for the preparation of secondary alkyl arylsulfones by this unexpected C--C bondcleavage reaction using excess Grignard reagent.展开更多
Asymmetric hydrogenation of α-keto Weinreb amides has been realized with [Ru((S)-Sunphos)(benzene)C1]C1 as the catalyst and CeC13·7H20 as the additive. A series of enantiopure -hydroxy Weinreb amides (up ...Asymmetric hydrogenation of α-keto Weinreb amides has been realized with [Ru((S)-Sunphos)(benzene)C1]C1 as the catalyst and CeC13·7H20 as the additive. A series of enantiopure -hydroxy Weinreb amides (up to 97% ee) have been obtained. Cata- lytic amount of CeC13·7H20 is essential for the high reactivity and enantioselectivity and the ratio of CeC13·7H20 to [Ru((S)-Sunphos)(benzene)C1]C1 plays an important role in the hydrogenation reaction.展开更多
Aim To synthesize the tripepide Weinreb amide Boc Asp(OBzl) β Ala Asp(OBzl) N(OMe)Me (7) as a useful precursor of aspartyl peptide aldehyde derivatives; Methods DCC, IBCF method was used for preparation of ...Aim To synthesize the tripepide Weinreb amide Boc Asp(OBzl) β Ala Asp(OBzl) N(OMe)Me (7) as a useful precursor of aspartyl peptide aldehyde derivatives; Methods DCC, IBCF method was used for preparation of Weinreb amide; N hydroxysuccinimide activated ester was used in peptide synthesis; and Boc as N protecting group of amino acid. Results Boc Asp(OBzl) N(OMe)Me (3), Boc β Ala Asp(OBzl) N(OMe)Me (5), and Boc Asp(OBzl) β Ala Asp(OBzl) N(OMe)Me (7) were synthesized successfully. Conclusion An useful precursor of tripeptide aspartyl aldehydes was synthesized.展开更多
文摘Weinreb酰胺是合成一些结构有意义或有生物活性的手性化合物的重要中间体,它可与有机金属试剂反应生成酮,又可被二异丁基铝氢(DIBAL-H),氢化铝锂(Li Al H4)等还原成醛,现已被普遍应用于全合成化学、药物化学以及生物有机化学等领域。因此,研究Weinreb酰胺的合成具有重大意义。本文综述了以羧酸、羧酸衍生物等为原料制备Weinreb酰胺的方法并对制备Weinreb酰胺的方法进行了展望。
基金National Natural Science Foundation of China (Grant No. 30772650 and 20772008)
文摘Peptidyl epoxyketones were potential antitumor agents due to their 20S proteasome inhibitory activities. Based on their structures and special inhibitory mechanism, a series of compounds were designed by linking the epoxyketone moiety (the Cterminal pharmacophore) and the peptide backbones. To make these compounds, we used a novel method to prepare the terminal α,β-unsaturated ketone, the crucial intermediate, from Weinreb amide with satisfactory yield (62%-65%).
文摘An unexpected decarboxamidation of a-arylsulfonyl Weinreb amides as a side reaction under the standardacylating conditions was found in Weirtreb amides chemistry. The control experiments for mechanism study disclosedthat a-sulfo group was necessary, and a-quaternary carbon was the key factor for the reaction. Meanwhile, an effi-cient method was established for the preparation of secondary alkyl arylsulfones by this unexpected C--C bondcleavage reaction using excess Grignard reagent.
文摘Asymmetric hydrogenation of α-keto Weinreb amides has been realized with [Ru((S)-Sunphos)(benzene)C1]C1 as the catalyst and CeC13·7H20 as the additive. A series of enantiopure -hydroxy Weinreb amides (up to 97% ee) have been obtained. Cata- lytic amount of CeC13·7H20 is essential for the high reactivity and enantioselectivity and the ratio of CeC13·7H20 to [Ru((S)-Sunphos)(benzene)C1]C1 plays an important role in the hydrogenation reaction.
文摘Aim To synthesize the tripepide Weinreb amide Boc Asp(OBzl) β Ala Asp(OBzl) N(OMe)Me (7) as a useful precursor of aspartyl peptide aldehyde derivatives; Methods DCC, IBCF method was used for preparation of Weinreb amide; N hydroxysuccinimide activated ester was used in peptide synthesis; and Boc as N protecting group of amino acid. Results Boc Asp(OBzl) N(OMe)Me (3), Boc β Ala Asp(OBzl) N(OMe)Me (5), and Boc Asp(OBzl) β Ala Asp(OBzl) N(OMe)Me (7) were synthesized successfully. Conclusion An useful precursor of tripeptide aspartyl aldehydes was synthesized.