New Methods for Stereoselective Addictions to Carbonyls

羰基立体选择性成瘾的新方法

• 批准号: 7486841
• 负责人: TAREK SAMMAKIA
• 金额: $ 25.75万
• 依托单位: UNIVERSITY OF COLORADO
• 依托单位国家: 美国
• 财政年份: 1993
• 资助国家: 美国
• 起止时间: 1993-07-01 至 2010-08-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/7486841
• 关键词: 3-hydroxybutanal; Acids; Aldehydes; Biological Factors; Compatible; Esters; Funding; Macrolide Antibiotics; Macrolides; Methods; Polyenes; Reaction; Staging; System; Time; Toluene; addiction; base; carbonyl compound; catalyst; cytotoxic; interest

DESCRIPTION (provided by applicant): The aims of this proposal are to discover new reactivity in addition reactions to carbonyl compounds, at times in the context of the total synthesis of natural products. Specific aims include completion of the synthesis of the oxo-polyene macrolide antibiotic RK-397. We have prepared a late stage intermediate and in the next funding period, we will complete this synthesis. We will also study an intramolecular vinylogous aldol reaction similar to the Yamamoto intermolecular vinylogous aldol and we will apply this method to the synthesis of the cytotoxic macrolide, arenolide. We will also study a new strategy for conducting intramolecular aldol reactions based on using C-silylated esters as the nucleophilic component. These compounds are compatible with aldehydes and should react only upon activation. We have also developed an interesting asymmetric O-nucleophilic catalyst for enantioselective acyl transfer in the past funding period. This catalyst currently displays s-values of up to 31 for the methanolysis of alpha-acetoxy N- acylthiazolidinethiones. We will explore this catalyst system in the upcoming funding period and delineate its scope and limitations.

描述(由申请人提供)：本建议的目的是在天然产物的全合成的背景下，有时在与羰基化合物的反应之外发现新的反应性。具体目标包括完成氧代多烯大环内酯类抗生素RK-397的合成。我们已经准备了一个后期中间体，在下一个资金阶段，我们将完成这一合成。我们还将研究类似于山本分子间乙烯基羟醛的分子内醇醛反应，并将该方法应用于细胞毒性大环内酯芳烯内酯的合成。我们还将研究一种基于C-硅烷化酯作为亲核成分进行分子内Aldol反应的新策略。这些化合物与醛是相容的，只有在活化时才能反应。在过去的资助期间，我们还开发了一种有趣的不对称O-亲核催化剂，用于对映体选择性酰基转移。该催化剂目前对α-乙酰氧基-N-酰基噻唑硫酮的甲醇分解反应的S值达31。我们将在即将到来的资助期探索这一催化剂系统，并说明其范围和局限性。

项目成果

O-nucleophilic amino alcohol acyl-transfer catalysts: the effect of acidity of the hydroxyl group on the activity of the catalyst.

O-亲核氨基醇酰基转移催化剂：羟基的酸性对催化剂活性的影响。

• DOI: 10.1021/ol035510n
• 发表时间: 2003
• 期刊: Organic letters.
• 作者: Wayman,KjirstenA;Sammakia,Tarek
• 通讯作者: Sammakia,Tarek

Highly selective asymmetric acetate aldol reactions of an N-acetyl thiazolidinethione reagent.

• DOI: 10.1021/ol036020y
• 发表时间: 2004-01
• 期刊: Organic letters
• 影响因子: 5.2
• 作者: Ying-chao Zhang;A. Phillips;T. Sammakia

Total synthesis of dermostatin A.

dermostatin A的全合成。

• DOI: 10.1021/jo2012658
• 发表时间: 2011
• 期刊: The Journal of organic chemistry
• 作者: Zhang,Yingchao;Arpin,CarolynnC;Cullen,AaronJ;Mitton-Fry,MarkJ;Sammakia,Tarek
• 通讯作者: Sammakia,Tarek

Use of thiazoles in the halogen dance reaction: application to the total synthesis of WS75624 B.

• DOI: 10.1021/jo0351217
• 发表时间: 2004-02
• 期刊: The Journal of organic chemistry
• 作者: Eric L. Stangeland;T. Sammakia

New inhibitors of colony spreading in Bacillus subtilis and Bacillus anthracis.

• DOI: 10.1016/j.bmcl.2011.06.082
• 发表时间: 2011-09-15
• 期刊: BIOORGANIC & MEDICINAL CHEMISTRY LETTERS
• 影响因子: 2.7
• 作者: Hao, Xin;Tam Nguyen;Kearns, Daniel B.;Arpin, Carolynn C.;Fall, Ray;Sammakia, Tarek
• 通讯作者: Sammakia, Tarek