2016
DOI: 10.1039/c5cc09162d
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Extremely efficient hydroboration of ketones and aldehydes by copper carbene catalysis

Abstract: A readily available copper carbene complex, (IPr)CuOtBu, catalyses the hydroboration of ketones and aldehydes even at very low catalyst loadings (0.1 mol%), in some cases with turnover frequencies exceeding 6000 h(-1). Carbonyl reduction occurs selectivitily in the presence of other reducible functional groups including alkenes, nitriles, esters, and alkyl chlorides.

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Cited by 99 publications
(50 citation statements)
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“…Thecorresponding alcohols 5 and 7, derived from radical ring closing and opening, respectively, were obtained in 68 %and 40 %yield. [9,18] Subsequently,n ucleophilic substitution takes place between B and ac oncomitantly formed copper hydride to yield aldehyde C.T of urnish the final silyl-protected alcohol E, aldehyde C undergoes reduction by established copper hydride catalysis via alkoxide intermediate D. [19] Based on this hypothetical mechanism, b-hydride elimination is avoided because of al ack of any metal-alkyl intermediates. Collectively,t hese observations are indicative of alkyl radical intermediates during catalysis.…”
mentioning
confidence: 99%
“…Thecorresponding alcohols 5 and 7, derived from radical ring closing and opening, respectively, were obtained in 68 %and 40 %yield. [9,18] Subsequently,n ucleophilic substitution takes place between B and ac oncomitantly formed copper hydride to yield aldehyde C.T of urnish the final silyl-protected alcohol E, aldehyde C undergoes reduction by established copper hydride catalysis via alkoxide intermediate D. [19] Based on this hypothetical mechanism, b-hydride elimination is avoided because of al ack of any metal-alkyl intermediates. Collectively,t hese observations are indicative of alkyl radical intermediates during catalysis.…”
mentioning
confidence: 99%
“…[17] Atom-transfer carbonylation to afford acyl iodide B then proceeds through acyl radical intermediate A. [9,18] Subsequently,n ucleophilic substitution takes place between B and ac oncomitantly formed copper hydride to yield aldehyde C.T of urnish the final silyl-protected alcohol E, aldehyde C undergoes reduction by established copper hydride catalysis via alkoxide intermediate D. [19] Based on this hypothetical mechanism, b-hydride elimination is avoided because of al ack of any metal-alkyl intermediates. As imilar ATCm echanism has been proposed for selected Cu-catalyzed carbonylative coupling reactions with tertiary alkyl halides.…”
Section: Angewandte Chemiementioning
confidence: 99%
“…[13] However, these protocols have no tolerance for other active functional groups such as nitro groups, nitriles, and amides. In addition, cata- lysts based on transition metals such as titanium, [17][18][19][20][21] manganese, [22] iron, [23] molybdenum, [24] rhodium, [25] ruthenium, [26] copper, [27] and zinc, [28] as well as on main group metals such as aluminum, [29] gallium, [30] germanium, [31] and tin, [31] are known for the hydroboration of carbonyl compounds. In addition, cata- lysts based on transition metals such as titanium, [17][18][19][20][21] manganese, [22] iron, [23] molybdenum, [24] rhodium, [25] ruthenium, [26] copper, [27] and zinc, [28] as well as on main group metals such as aluminum, [29] gallium, [30] germanium, [31] and tin, [31] are known for the hydroboration of carbonyl compounds.…”
Section: Introductionmentioning
confidence: 99%
“…[10] Recent reports from the laboratories of Okuda, [14] Hill, [15] Sen, [16] and others have utilized new alkali metal and alkaline earth (Ae) metal catalysts for the hydroboration of carbonyl compounds. In addition, cata- lysts based on transition metals such as titanium, [17][18][19][20][21] manganese, [22] iron, [23] molybdenum, [24] rhodium, [25] ruthenium, [26] copper, [27] and zinc, [28] as well as on main group metals such as aluminum, [29] gallium, [30] germanium, [31] and tin, [31] are known for the hydroboration of carbonyl compounds. Very recently, the groups of Marks and of Shen reported on the use of active rare-earth metals La [32] and Yb [33] as catalysts for the hydroboration of carbonyl compounds.…”
Section: Introductionmentioning
confidence: 99%