Asymmetric carbon-carbon formation based on soft metal-hard anion conjugated catalysis

软金属-硬阴离子共轭不对称催化剂，如CuF和CuOR表现出独特的反应活性。与多用途的碳亲核试剂结合，如烯丙基硅烷、烯丙基硼酸盐、烯酮硅基缩醛、烯丙基硅烷、烯丙基硼酸盐、芳基硅烷和芳基硼酸盐，它们迅速将硬阴离子转移到硬金属（Si和B）上。由此产生的铜硅酸盐或硼酸盐可以将软碳亲核试剂转移回软铜，生成高度亲核的铜基亲核试剂，如烯丙基铜、烯醇化铜、烯基铜和烯基铜。手性亲核试剂是用手性膦生成的。铜基亲核试剂反应性强，实现了酮和酮亚胺的催化不对称加成。将软金属-硬阴离子共轭不对称催化的概念推广到烯丙烯酯、酮类和丙酸酯的三组分反应。以铜为催化剂，以聚硼酸乙酯为原料，经转金属反应生成氢化铜。氢化铜化学选择性地还原了烯丙烯酯，生成了烯醇酸铜。铜烯酸酯对映选择性地加到酮体上。重要的是，反应模式可通过手性膦结构进行调节。以DTBM-SEGPHOS为配体，反应通过γ-顺式选择性进行。而α-加合物是选择性地以塔尼福斯为配体生成的。这些结果表明，手性催化剂可以控制多组分反应的反应模式。

Soft metal-hard anion conjugated asymmetric catalysts, such as CuF and CuOR display unique reactivity. Combined with versatile carbon nucleophiles, such as allylsilanes, allylboronates, ketene silyl acetals, alkenylsilanes, alkenylboronates, arylsilanes, and arylboronates, they quickly transfer hard anion onto hard metals (Si and B). Resulting Cu silicates or borates can transfer soft carbon nucleophiles back to soft Cu, generating highly nucleophilic Cu-based nucleophiles, such as allylcopper, copper enolates, alkenylcopper, and aiylcopper. Chiral nucleophiles are to be generated using chiral phosphines. The Cu-based nucleophiles are highly reactive, and catalytic asymmetric addition to ketones and ketoimines were realized. The concept of soft metal-hard anion conjugated asymmetric catalysis was extended to three-component reaction of an allenic ester, ketones, and pinacolboronate. From the Cu catalyst and pinacolboronate, copper hydride was generated through transmetalation. The copper hydride reduced allenic ester chemoselectively, and copper enolate was generated. The copper enolate added to ketones enantioselectively. Importantly, reaction pattern was tunable by the chiral phosphine structure. Using DTBM-SEGPHOS as a ligand, the reaction proceeded through γ-cis selective manner. Whereas, α-adduct was selectively produced using Taniaphos as a ligand. These results demonstrated that the reaction pattern of the multi-component reaction can be controlled by the chiral catalyst.