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Enantioselective 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds catalyzed by rhodium(I)-chiral phosphoramidite complexes
| Title: | Enantioselective 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds catalyzed by rhodium(I)-chiral phosphoramidite complexes |
| Authors: | Kurihara, Kazunori Browse this author | | Sugishita, Noriyuki Browse this author | | Oshita, Kengo Browse this author | | Piao, Dongguo Browse this author | | Yamamoto, Yasunori Browse this author →KAKEN DB | | Miyaura, Norio Browse this author |
| Keywords: | Arylboronic acids | | Rhodium catalyst | | Phosphoramidite | | Asymmetric | | Conjugate addition |
| Issue Date: | 1-Jan-2007 |
| Publisher: | Elsevier |
| Journal Title: | Journal of Organometallic Chemistry |
| Volume: | 692 |
| Issue: | 1-3 |
| Start Page: | 428 |
| End Page: | 435 |
| Publisher DOI: | 10.1016/j.jorganchem.2006.04.042 |
| Abstract: | A chiral bidentate phosphoramidite (5a) was synthesized from Shibasaki’s linked-(R)-BINOL and P(NMe2)3 as a new ligand for rhodium(I)-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds. The effects of 5a and Feringa’s monodentate phosphoramidite (4, R1, R2 = Et) on the yields and enantioselectivities were fully investigated. The reaction was significantly accelerated in the presence of a base such as KOH and Et3N, allowing the reaction to be completed at the lower temperatures than 50 °C. The addition to cyclic enones such as 2-cyclopentenone, 2-cyclohexenone and 2-cycloheptenone at 50 °C in the presence of an [Rh(coe)2Cl]2-4 (R1, R2 = Et) complex resulted in enantioselectivities up to 98%, though it was less effective for acyclic enones (0–70% ee). On the other hand, a complex between [Rh(nbd)2]BF4 and 5a completed the addition to cyclic enones within 2 h at room temperature in the presence of Et3N with 86–99% yields and 96–99.8% ee. This catalyst was also effective for acyclic enones, resulting in 62–98% yields and 66–94% ee. The 1,4-additions of arylboronic acids to unsaturated lactones and acyclic esters with rhodium(I)-phosphoramidites complexes were also investigated. |
| Relation: | http://www.sciencedirect.com/science/journal/0022328X |
| Type: | article (author version) |
| URI: | http://hdl.handle.net/2115/18877 |
| Appears in Collections: | 工学院・工学研究院 (Graduate School of Engineering / Faculty of Engineering) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)
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Submitter: 宮浦 憲夫
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