COMPLEX CARBOCYCLE BY PHOTOCYCLOADDITION

通过光环负载形成复合碳环

• 批准号: 2444774
• 负责人: Scott McNeill Sieburth
• 金额: $ 17.74万
• 依托单位: STATE UNIVERSITY NEW YORK STONY BROOK
• 依托单位国家: 美国
• 财政年份: 1991
• 资助国家: 美国
• 起止时间: 1991-01-01 至 1998-09-30
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/2444774
• 关键词: chemical addition; chemical structure function; chemical synthesis; cyclic ketone; cyclization; cyclopentane; dimer; paclitaxel; photochemistry

The [4+4] photodimerization of 2-pyridones is as efficient method for preparing cyclooctadienes strategically functionalized for synthetic challenges such as taxol and the fusicoccanes. This single-step method for preparing complex structure from simple aromatic precursors proceeds with high region- and stereochemical control, but has not been exploited synthetically. Our studies of a previously untested intramolecular version of this reaction has laid the groundwork for applications to total synthesis. Two intramolecular approaches to taxol, and a synthesis of the complex fusicoccane are proposed. A preliminary study has demonstrated a selective intermolecular reaction of 4-alkoxy-2-pyridone with 2-pyridone, predicated on the inability to undergo [4+4] photodimerization. This new approach to control of the [4+4] reaction, in the absence of a tether, allows for other important targets to be addressed. Synthesis of the antibiotic pentalenolactone and an approach to taxol are proposed.

2-吡啶酮的[4+4]光二聚化是有效的方法 制备策略性化合成功能化的环链蛋白酶 紫杉醇和fusicoccanes等挑战。 这个单步方法 从简单的芳香前体制备复杂的结构 具有高区域和立体化学控制，但尚未被利用 合成。 我们对以前未经测试的分子的研究 此反应的版本为应用程序奠定了基础 总合成。 两种分子内方法的紫杉醇和一种合成 提出了复杂的fusicocacan。 一项初步研究表明选择性分子间反应 具有2-吡啶酮的4-烷氧基-2-吡啶酮，这是基于无法 进行[4+4]光构化。 这种控制的新方法 [4+4]在没有系绳的情况下，反应允许其他重要的 要解决的目标。 合成抗生素丙烯酸酯酮的合成 并提出了一种方法。

项目成果

Photoreactivity of 2-pyridones with furan, benzene, and naphthalene. Inter- and intramolecular photocycloadditions.

2-吡啶酮与呋喃、苯和萘的光反应性。

• DOI: 10.1021/jo9918394
• 发表时间: 2000
• 期刊: The Journal of organic chemistry
• 作者: Sieburth,SM;McGeeJr,KF;Zhang,F;Chen,Y
• 通讯作者: Chen,Y

A [4 + 4] 2-pyridone approach to taxol. 3. Stereocontrol during elaboration of the cyclooctane.

• DOI: 10.1021/jo005532c
• 发表时间: 2000-09
• 期刊: The Journal of organic chemistry
• 作者: Y. G. Lee;K. Mcgee;J. Chen;D. Rucando;S. Sieburth

Solvent-dependent stereoselectivity of bis-2-pyridone [4 + 4] photocycloaddition is due to H-bonded dimers.

双-2-吡啶酮[4 4]光环加成的溶剂依赖性立体选择性是由于氢键二聚体造成的。

• DOI: 10.1021/ol991058p
• 发表时间: 1999
• 期刊: Organic letters
• 影响因子: 5.2
• 作者: Sieburth,SM;McGeeJr,KF
• 通讯作者: McGeeJr,KF