Pathways to Functionalized Heterocycles: Propargyl Rearrangement using B(C6F5)3

被引：28

作者：

Wilkins, Lewis C. ^{[1
]}

Wieneke, Philipp ^{[1
]}

Newman, Paul D. ^{[1
]}

Kariuki, Benson M. ^{[1
]}

Rominger, Frank ^{[2
]}

Hashmi, A. Stephen K. ^{[2
,3
]}

Hansmann, Max M. ^{[2
]}

Melen, Rebecca L. ^{[1
]}

机构：

[1] Cardiff Univ, Sch Chem, Cardiff CF10 3AT, Cymru, Wales

[2] Heidelberg Univ, Inst Organ Chem, D-69120 Heidelberg, Germany

[3] King Abdulaziz Univ, Dept Chem, Jeddah 21589, Saudi Arabia

来源：

ORGANOMETALLICS | 2015年 / 34卷 / 21期

关键词：

GOLD-CATALYZED SYNTHESIS; CYCLIZATION; COMPLEXES; ALKYNES; POTENT; DIBENZOPENTALENES; DERIVATIVES; OXAZOLONES; AGONISTS; ESTERS;

D O I：

10.1021/acs.organomet.5b00753

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The reactions of propargyl amides, ureas, carbamates, and carbonates with B(C6F5)(3) proceed via an intramolecular 5-exo-dig cyclization across the alkyne unit to yield the corresponding vinyl borate species. The generated se carbocation is stabilized by the flanking heteroatoms, allowing for isolation of oxazoline intermediates. The fate of these intermediates is strongly dependent upon the propargyl-functionalized starting material, with the carbamates and carbonates undergoing a ring-opening mechanism (propargyl rearrangement) to give cyclic allylboron compounds, while prolonged heating of the urea derivatives shows evidence of oxazole formation. In a deviation away from the reactivity of carbamates stated previously, the undergoes dealkylation at the benzylic position, liberating 5-methyloxazol-2-(3H)-one. Me benzyl carbamate substrate

引用

页码：5298 / 5309

页数：12

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