“…Moreover, we further expanded the success of this synergetic catalysis system to the more challenging four-component reaction radical carbonylative carbocyanation. Notably, CO would coordinatively saturate the Cu center and/or compete with cyanides and chiral ligands, thus making the chiral Cu catalyst ineffective or making radical carbonylative carbocyanation unordered. − To our delight, preliminary experiments indicated that the four-component reactions with 1,3-diene 1a or 1,3-enyne 8c occurred in an orderly manner, affording chiral allyl ketocyanide 10 and chiral propargyl ketocyanide 11 in moderate yields and high enantioselectivities (Figure b, 10 : 46% yield and 91% ee; 11 : 48% yield and 88% ee).…”
1,3-Dienes are readily available feedstocks that are widely used in the laboratory and industry. However, the potential of converting 1,3-dienes into value-added products, especially chiral products, has not yet been fully exploited. By synergetic photoredox/copper catalysis, we achieve the first visible-light-induced, enantioselective carbocyanation of 1,3-dienes by using carboxylic acid derivatives and trimethylsilyl cyanide. Under mild and neutral conditions, a diverse range of chiral allyl cyanides are produced in generally good efficiency and with high enantioselectivity from bench-stable and user-safe chemicals. Moreover, preliminary results also confirm that this success can be expanded to 1,3-enynes and the four-component carbonylative carbocyanation of 1,3-dienes and 1,3-enynes.
“…Moreover, we further expanded the success of this synergetic catalysis system to the more challenging four-component reaction radical carbonylative carbocyanation. Notably, CO would coordinatively saturate the Cu center and/or compete with cyanides and chiral ligands, thus making the chiral Cu catalyst ineffective or making radical carbonylative carbocyanation unordered. − To our delight, preliminary experiments indicated that the four-component reactions with 1,3-diene 1a or 1,3-enyne 8c occurred in an orderly manner, affording chiral allyl ketocyanide 10 and chiral propargyl ketocyanide 11 in moderate yields and high enantioselectivities (Figure b, 10 : 46% yield and 91% ee; 11 : 48% yield and 88% ee).…”
1,3-Dienes are readily available feedstocks that are widely used in the laboratory and industry. However, the potential of converting 1,3-dienes into value-added products, especially chiral products, has not yet been fully exploited. By synergetic photoredox/copper catalysis, we achieve the first visible-light-induced, enantioselective carbocyanation of 1,3-dienes by using carboxylic acid derivatives and trimethylsilyl cyanide. Under mild and neutral conditions, a diverse range of chiral allyl cyanides are produced in generally good efficiency and with high enantioselectivity from bench-stable and user-safe chemicals. Moreover, preliminary results also confirm that this success can be expanded to 1,3-enynes and the four-component carbonylative carbocyanation of 1,3-dienes and 1,3-enynes.
“…A possible pathway was proposed based on previous studies 15,16,19 and the experimental results discussed above (Scheme 5). At first, bis(pinacolato)diboron (B 2 pin 2 ) transferred a boryl group to the copper center in the presence of base.…”
Cyclopropanes, especially substituted cyclopropanes play important roles in many pharmaceuticals and organic synthesis. In this communication, we introduced a new strategy for the synthesis of diborylated cyclopropanes via a copper-catalyzed...
“…22,23 Likewise, Fe-bound acyl units can act as structural models of the Fe hydrogenase active site. 24 For copper, however, these unstable species have been proposed as intermediates in Cu-catalysed reactions such as borocarbonylation and amidation, 25 but have not been isolated, due to their propensity to undergo facile rearrangement.…”
We report on the insertion of alkynes into heterometallic M–M' bonds, producing (aluminylalkenyl)copper compounds which possess differential reactivity at the two derived M–C functions. Uniquely, this system is capable of...
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