Highly Enantioselective Reductive Cyclization of Acetylenic Aldehydes via Rhodium Catalyzed Asymmetric Hydrogenation
- 1 August 2006
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 128 (33) , 10674-10675
- https://doi.org/10.1021/ja0637954
Abstract
Catalytic hydrogenation of acetylenic aldehydes 1a − 12a using chirally modified cationic rhodium catalysts enables highly enantioselective reductive cyclization to afford cyclic allylic alcohols 1b − 12b. Using an achiral hydrogenation catalyst, the chiral racemic acetylenic aldehydes 13a − 15a engage in highly syn-diastereoselective reductive cyclizations to afford cyclic allylic alcohols 13b − 15b. Ozonolysis of cyclization products 7b and 9b allows access to optically enriched α-hydroxy ketones 7c and 9c. Reductive cyclization of enyne 7a under a deuterium atmosphere provides the monodeuterated product deuterio-7b, consistent with a catalytic mechanism involving alkyne−carbonyl oxidative coupling followed by hydrogenolytic cleavage of the resulting oxametallacycle. These hydrogen-mediated transformations represent the first examples of the enantioselective reductive cyclization of acetylenic aldehydes.Keywords
This publication has 17 references indexed in Scilit:
- Access to Macrocyclic Endocyclic and Exocyclic Allylic Alcohols by Nickel-Catalyzed Reductive Cyclization of YnalsJournal of the American Chemical Society, 2005
- New Route to Biaryl Phosphanes with Axial Chirality as Ligands for Enantioselective HydrogenationsAdvanced Synthesis & Catalysis, 2004
- Hydrogen-Mediated C−C Bond Formation: Catalytic Regio- and Stereoselective Reductive Condensation of α-Keto Aldehydes and 1,3-EnynesJournal of the American Chemical Society, 2004
- Ligand-Dependent Scope and Divergent Mechanistic Behavior in Nickel-Catalyzed Reductive Couplings of Aldehydes and AlkynesJournal of the American Chemical Society, 2004
- First Catalytic Reductive Coupling of 1,3-Diynes to Carbonyl Partners: A New Regio- and Enantioselective C−C Bond Forming HydrogenationJournal of the American Chemical Society, 2003
- Catalytic Asymmetric Reductive Coupling of Alkynes and Aldehydes: Enantioselective Synthesis of Allylic Alcohols and α-Hydroxy KetonesJournal of the American Chemical Society, 2003
- Nickel-Catalyzed Preparation of Bicyclic Heterocycles: Total Synthesis of (+)-Allopumiliotoxin 267A, (+)-Allopumiliotoxin 339A, and (+)-Allopumiliotoxin 339BJournal of the American Chemical Society, 2000
- A New Stereoselective Method for the Preparation of Allylic AlcoholsJournal of the American Chemical Society, 1997
- Titanium-Catalyzed Reductive Cyclization of .delta.,.epsilon.-Unsaturated Ketones and AldehydesJournal of the American Chemical Society, 1995
- Extremely Chemoselective Silylformylation and Silylcarbocyclization of AlkynalsJournal of the American Chemical Society, 1994