A General Bifunctional Catalyst for the Anti-Markovnikov Hydration of Terminal Alkynes to Aldehydes Gives Enzyme-Like Rate and Selectivity Enhancements

A General Bifunctional Catalyst for the Anti-Markovnikov Hydration of Terminal Alkynes to Aldehydes Gives Enzyme-Like Rate and Selectivity Enhancements

A new, bifunctional catalyst for anti-Markovnikov hydration of terminal alkynes to aldehydes (6) allows practical room-temperature hydration of alkyl-substituted alkynes. Other outstanding features include near-quantitative aldehyde yields from both alkyl- and aryl-substituted alkynes and wide funct...

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Veröffentlicht in:Journal of the American Chemical Society 2004-10, Vol.126 (39), p.12232-12233
Hauptverfasser: Grotjahn, Douglas B, Lev, Daniel A
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Chemistry
Exact sciences and technology
Organic chemistry
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container_issue 39
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container_title Journal of the American Chemical Society
container_volume 126
creator Grotjahn, Douglas B
Lev, Daniel A
description A new, bifunctional catalyst for anti-Markovnikov hydration of terminal alkynes to aldehydes (6) allows practical room-temperature hydration of alkyl-substituted alkynes. Other outstanding features include near-quantitative aldehyde yields from both alkyl- and aryl-substituted alkynes and wide functional group tolerance. The uncatalyzed rate of alkyne hydration is measured for the first time, showing the enzyme-like rate and selectivity enhancements of aldehyde formation by 6. For aldehyde formation, an uncatalyzed rate 600 000 years. The catalyzed rate is up to 23.8 mol (mol 6)-1 h-1 and 10 000:1 ratio in favor of aldehyde. Changes in rate and selectivity induced by 6 are thus >2.4 × 1011 and 300 000, respectively.
doi_str_mv 10.1021/ja046360u
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title A General Bifunctional Catalyst for the Anti-Markovnikov Hydration of Terminal Alkynes to Aldehydes Gives Enzyme-Like Rate and Selectivity Enhancements
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