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Engaging Aldehydes in CuH-Catalyzed Reductive Coupling Reactions: Stereoselective Allylation with Unactivated 1,3-Diene Pronucleophiles.
Angew Chem Int Ed Engl. 2019 11 18; 58(47):17074-17080.AC

Abstract

Recently, CuH-catalyzed reductive coupling processes involving carbonyl compounds and imines have become attractive alternatives to traditional methods for stereoselective addition because of their ability to use readily accessible and stable olefins as surrogates for organometallic nucleophiles. However, the inability to use aldehydes, which usually reduce too rapidly in the presence of copper hydride complexes to be viable substrates, has been a major limitation. Shown here is that by exploiting relative concentration effects through kinetic control, this intrinsic reactivity can be inverted and the reductive coupling of 1,3-dienes with aldehydes achieved. Using this method, both aromatic and aliphatic aldehydes can be transformed into synthetically valuable homoallylic alcohols with high levels of diastereo- and enantioselectivities, and in the presence of many useful functional groups. Furthermore, using a combination of theoretical (DFT) and experimental methods, important mechanistic features of this reaction related to stereo- and chemoselectivities were uncovered.

Authors+Show Affiliations

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts, 02139, USA.Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts, 02139, USA.Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts, 02139, USA.Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts, 02139, USA.

Pub Type(s)

Journal Article
Research Support, N.I.H., Extramural
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

31552701

Citation

Li, Chengxi, et al. "Engaging Aldehydes in CuH-Catalyzed Reductive Coupling Reactions: Stereoselective Allylation With Unactivated 1,3-Diene Pronucleophiles." Angewandte Chemie (International Ed. in English), vol. 58, no. 47, 2019, pp. 17074-17080.
Li C, Shin K, Liu RY, et al. Engaging Aldehydes in CuH-Catalyzed Reductive Coupling Reactions: Stereoselective Allylation with Unactivated 1,3-Diene Pronucleophiles. Angew Chem Int Ed Engl. 2019;58(47):17074-17080.
Li, C., Shin, K., Liu, R. Y., & Buchwald, S. L. (2019). Engaging Aldehydes in CuH-Catalyzed Reductive Coupling Reactions: Stereoselective Allylation with Unactivated 1,3-Diene Pronucleophiles. Angewandte Chemie (International Ed. in English), 58(47), 17074-17080. https://doi.org/10.1002/anie.201911008
Li C, et al. Engaging Aldehydes in CuH-Catalyzed Reductive Coupling Reactions: Stereoselective Allylation With Unactivated 1,3-Diene Pronucleophiles. Angew Chem Int Ed Engl. 2019 11 18;58(47):17074-17080. PubMed PMID: 31552701.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Engaging Aldehydes in CuH-Catalyzed Reductive Coupling Reactions: Stereoselective Allylation with Unactivated 1,3-Diene Pronucleophiles. AU - Li,Chengxi, AU - Shin,Kwangmin, AU - Liu,Richard Y, AU - Buchwald,Stephen L, Y1 - 2019/10/22/ PY - 2019/08/28/received PY - 2019/09/23/revised PY - 2020/11/18/pmc-release PY - 2019/9/26/pubmed PY - 2020/9/22/medline PY - 2019/9/26/entrez KW - aldehydes KW - allylic compounds KW - copper KW - dienes KW - reductive coupling SP - 17074 EP - 17080 JF - Angewandte Chemie (International ed. in English) JO - Angew. Chem. Int. Ed. Engl. VL - 58 IS - 47 N2 - Recently, CuH-catalyzed reductive coupling processes involving carbonyl compounds and imines have become attractive alternatives to traditional methods for stereoselective addition because of their ability to use readily accessible and stable olefins as surrogates for organometallic nucleophiles. However, the inability to use aldehydes, which usually reduce too rapidly in the presence of copper hydride complexes to be viable substrates, has been a major limitation. Shown here is that by exploiting relative concentration effects through kinetic control, this intrinsic reactivity can be inverted and the reductive coupling of 1,3-dienes with aldehydes achieved. Using this method, both aromatic and aliphatic aldehydes can be transformed into synthetically valuable homoallylic alcohols with high levels of diastereo- and enantioselectivities, and in the presence of many useful functional groups. Furthermore, using a combination of theoretical (DFT) and experimental methods, important mechanistic features of this reaction related to stereo- and chemoselectivities were uncovered. SN - 1521-3773 UR - https://www.unboundmedicine.com/medline/citation/31552701/Engaging_Aldehydes_in_CuH_Catalyzed_Reductive_Coupling_Reactions:_Stereoselective_Allylation_with_Unactivated_13_Diene_Pronucleophiles_ L2 - https://doi.org/10.1002/anie.201911008 DB - PRIME DP - Unbound Medicine ER -