Asymmetric Nitrocyclopropanation of α‐Substituted α, β‐Enals Catalyzed by Diphenylprolinol Silyl Ether for the Construction of All‐Carbon Quaternary ­Stereogenic Centers. Issue 26 (6th August 2015)

• Record Type: Journal Article
• Authors: Hayashi, Yujiro; Yamazaki, Tatsuya; Nakanishi, Yuki; Ono, Tsuyoshi; Taniguchi, Tohru; Monde, Kenji; Uchimaru, Tadafumi
• Is Part Of: European journal of organic chemistry. Issue 26(2015)
• Page Start: 5747
• Page End: 5754
• Publication Date: 2015-08-06
• Subjects: Organocatalysis -- Asymmetric synthesis -- Small ring systems -- Cyclo­propanation -- Chirality; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201500838
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract: The diphenylprolinol silyl ether mediated asymmetric nitrocyclopropanation of α‐substituted α, β‐unsaturated aldehydes with bromonitromethane, followed by base‐promoted isomerization was found to afford trans ‐nitrocyclopropanecarbaldehydes with all‐carbon quaternary stereogenic centers with excellent diastereo‐ and enantioselectivities. DFT calculations indicated that the s‐trans conformer of the iminium ion intermediate is more stable than the s‐cis conformer. In addition, nucleophilic attack of the bromonitromethane anion to the iminium ion intermediate was calculated to occur preferentially from the opposite side of the bulky substituents of the pyrrolidine iminium intermediate. Abstract : The diphenylprolinol silyl ether mediated asymmetric nitrocyclopropanation of α‐substituted α, β‐unsaturated aldehydes with bromonitromethane, followed by base‐promoted isomerization affords trans ‐nitrocyclopropanecarbaldehydes with all‐carbon quaternary stereogenic centers with excellent diastereo‐ and enantioselectivities. The reaction is believed to proceed via an s‐trans iminium ion intermediate.