Tandem Z-Selective Cross-Metathesis/Dihydroxylation: Synthesis of anti-1,2-Diols

被引:25
作者
Dornan, Peter K. [1 ]
Wickens, Zachary K. [1 ]
Grubbs, Robert H. [1 ]
机构
[1] CALTECH, Div Chem & Chem Engn, Pasadena, CA 91125 USA
基金
美国国家科学基金会;
关键词
anti-diols; dihydroxylation; metathesis; tandem reactions; Z-selectivity; RING-CLOSING METATHESIS; OLEFIN METATHESIS; RUTHENIUM CATALYSTS; ASYMMETRIC DIHYDROXYLATION; ENANTIOSELECTIVE SYNTHESIS; OPENING/CROSS-METATHESIS; ISOMERIZATION SEQUENCE; HYDROGENATION; COMPLEXES; OXIDATION;
D O I
10.1002/anie.201501505
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A stereoselective synthesis of anti-1,2-diols has been developed using a multitasking Ru catalyst in an assisted tandem catalysis protocol. A cyclometalated Ru complex catalyzes first a Z-selective cross-metathesis of two terminal olefins, followed by a stereospecific dihydroxylation. Both steps are catalyzed by Ru, as the Ru complex is converted to a dihydroxylation catalyst upon addition of NaIO4. A variety of olefins were transformed into valuable, highly functionalized, and stereodefined molecules. Mechanistic experiments were performed to probe the nature of the oxidation step and catalyst inhibition pathways. These experiments point the way to more broadly applicable tandem catalytic transformations.
引用
收藏
页码:7134 / 7138
页数:5
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