Linear‐selective hydroformylation of vinyl ether using Rh (acac)(2,2′‐bis{(di[1H‐indol‐1‐yl]phosphanyl)oxy}‐1,1′‐binaphthalene) – Possible way to synthesize 1,3‐propanediol,Applied Organometallic Chemistry

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Linear‐selective hydroformylation of vinyl ether using Rh (acac)(2,2′‐bis{(di[1H‐indol‐1‐yl]phosphanyl)oxy}‐1,1′‐binaphthalene) – Possible way to synthesize 1,3‐propanediol
Applied Organometallic Chemistry ( IF 3.7 ) Pub Date : 2020-07-19 , DOI: 10.1002/aoc.5863
Kefeng Wan ₁ , Jiangui Zhao ₁ , Song Qin ₁ , Xueli Zheng ₁ , Haiyan Fu ₁ , Ruixiang Li ₁ , Hua Chen ₁ , Jijun Yang ₂ , Chunji Yang ₃

Affiliation

Three bidentate phosphoramidite ligands were synthesized, characterized, and employed in Rh‐catalyzed hydroformylation of vinyl ethers. The complex Rh(acac)(2,2′‐bis{(di[1H‐indol‐1‐yl]phosphanyl)oxy}‐1,1′‐binaphthalene} (acac = acetylacetone) (Rh‐L4) was also synthesized and characterized. Rh‐L4 showed good regioselectivity for the hydroformylation of vinyl ethers under mild reaction conditions: 2 MPa of syngas, 1:1 (H₂/CO) substrate/catalyst molar ratio 1000:1, and 60 °C. The linear selectivity was up to 98%, and in most cases was about 80%, with no hydrogenation product formation observed, which could be a potential way to synthesize 1,3‐propanediol. A mechanism study including density functional theory computational analysis showed that both Rh–H and CO insertion steps in the hydroformylation of vinyl ether were linear‐preferred in our catalyst system.

中文翻译：

使用Rh（acac）（2,2'-bis {（二[1H-吲哚-1-基]磷酰基]氧基} -1,1'-联萘）进行乙烯基醚的线性选择性加氢甲酰化–合成1， 3-丙二醇

合成，表征了三种双齿亚磷酰胺配体，并将其用于乙烯基醚的Rh催化加氢甲酰化。还合成了复杂的Rh（acac）（2,2'-bis {（二[1H-吲哚-1-基]膦基]氧基} -1,1'-联萘}（acac =乙酰丙酮）（Rh- L4） Rh- L4在温和的反应条件下对乙烯基醚的加氢甲酰化反应显示出良好的区域选择性：2 MPa的合成气，1：1（H ₂/ CO）底物/催化剂的摩尔比为1000：1，温度为60°C。线性选择性高达98％，在大多数情况下约为80％，没有观察到氢化产物的形成，这可能是合成1,3-丙二醇的潜在方法。包括密度泛函理论计算分析在内的机理研究表明，在我们的催化剂体系中，乙烯基醚加氢甲酰化中的Rh–H和CO插入步骤都是线性的。

更新日期：2020-09-14

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