Generation of Medium-Ring Cycloalkynes by Ring Expansion of Vinylogous Acyl Triflates

被引：44

作者：

Tummatorn, Jumreang ^{[1
]}

Dudley, Gregory B. ^{[1
]}

机构：

[1] Florida State Univ, Dept Chem & Biochem, Tallahassee, FL 32306 USA

来源：

ORGANIC LETTERS | 2011年 / 13卷 / 06期

基金：

美国国家科学基金会;

关键词：

CARBON BOND-CLEAVAGE; FREE CLICK CHEMISTRY; ACETYLENIC KETONES; COPPER-FREE; FRAGMENTATION; CONDENSATION; ELIMINATION; REDUCTIONS; ALKYLATION; PHEROMONE;

D O I：

10.1021/ol2003308

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Reductive cyclization of aryl and vinyl iodides tethered to vinylogous acyl trifiates (VATS) induces a ring-expanding fragmentation to provide cyclic alkynyl ketones, including strained nine-membered cycloalkynes, in fair to excellent yield. The tandem cyclization/C-C bond-cleavage is Initiated under carefully optimized conditions by halogen metal exchange in the presence of carbonyl and vinyl triflate functionality. A modified protocol for alkylation of 1,3-cyclohexanedione is described for preparing the relevant VAT substrates.

引用

页码：1572 / 1575

页数：4

共 53 条

[1]

[Anonymous], MODERN ACETYLENE CHE

[2]

Baskin JM, 2010, ALDRICHIM ACTA, V43, P15

[3] Preparation of Tethered Aldehyde Ynoates and Ynones by Ring Fragmentation of Cyclic γ-Oxy-β-hydroxy-α-diazo Carbonyls [J].

Bayir, Ali ;

Draghici, Cristian ;

Brewer, Matthias .

JOURNAL OF ORGANIC CHEMISTRY, 2010, 75 (02) :296-302

[4] Tetrazine ligation: Fast bioconjugation based on inverse-electron-demand Diels-Alder reactivity [J].

Blackman, Melissa L. ;

Royzen, Maksim ;

Fox, Joseph M. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (41) :13518-+

[5]

Brandsma L., 1988, PREPARATIVE ACETYLEN, V2nd

[6] NEW PREPARATION OF ACETYLENIC KETONES AND APPLICATION TO SYNTHESIS OF EXO-BREVICOMIN, PHEROMONE FROM DENDROCTONUS-BREVICOMIS [J].

COKE, JL ;

WILLIAMS, HJ ;

NATARAJAN, S .

JOURNAL OF ORGANIC CHEMISTRY, 1977, 42 (14) :2380-2382

[7] Unusual Approach to Branched 3-Alkynylamides and to 1,5-Dihydropyrrol-2-ones [J].

Dias-Jurberg, Igor ;

Gagosz, Fabien ;

Zard, Samir Z. .

ORGANIC LETTERS, 2010, 12 (03) :416-419

[8]

Diederich F, 2005, ACETYLENE CHEMISTRY: CHEMISTRY, BIOLOGY AND MATERIAL SCIENCE, pV

[9] Lewis acid promoted carbon-carbon bond cleavage of γ-silyloxy-β-hydroxy-α-diazoesters [J].

Draghici, Cristian ;

Brewer, Matthias .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (12) :3766-+

[10] An Efficient Synthetic Approach to Polycyclic 2,5-Dihydropyrroles from α-Silyloxy Ketones [J].

Draghici, Cristian ;

Huang, Qiufeng ;

Brewer, Matthias .

JOURNAL OF ORGANIC CHEMISTRY, 2009, 74 (21) :8410-8413

← 1 2 3 4 5 6 →