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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
Author(s) -
Wan Kefeng,
Zhao Jiangui,
Qin Song,
Zheng Xueli,
Fu Haiyan,
Li Ruixiang,
Chen Hua,
Yang Jijun,
Yang Chunji
Publication year - 2020
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.5863
Subject(s) - hydroformylation , chemistry , acetylacetone , regioselectivity , vinyl ether , catalysis , phosphoramidite , medicinal chemistry , selectivity , denticity , propanediol , carbonylation , organic chemistry , rhodium , polymer chemistry , carbon monoxide , copolymer , dna , biochemistry , polymer , oligonucleotide , crystal structure
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 (H 2 /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.