Mo-Catalyzed Asymmetric Allylic Alkylation Enabling the Con-struction of Highly Enantioenriched 1,4-Dicarbonyl Scaffolds
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1.
California Institute of Technology
Abstract
Herein, we report a Mo-catalyzed allylic alkylation that couples malonate nucleophiles with linear, tri-substituted allylic electrophiles, followed by a rapid ozonolysis. The process delivers 1,4-dicarbonyl compounds con-taining an -quaternary aldehyde motif with excellent enantioselectivity. This constitutes the first example of a Mo-catalyzed asymmetric allylic alkylation to form an electrophile-derived all-carbon quaternary stereocenter. The reac-tivity and stereoselectivity of the process was enabled by the invention of ShabyDACH, a novel C1-symmetric diamino-cyclohexane (DACH) pyridyl ligand. The utility of this transformation was demonstrated through a series of diverse synthetic transformations.
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Funding
The NIH-NIGMS (R35GM145239), Heritage Medical Research Investigators Program, and Caltech are thanked for their support of our research program.
Acknowledgement
The authors would like to thank Dr. Scott Virgil (Caltech) for assistance with instrumentation and mass spectrometry and Dr. Mike Takase for assistance with x-ray crystallography. FAM would like to dedicate this article to his late aunt Shabnam.
Supplemental Material
Experimental and spectral data
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Additional details
- National Institute of General Medical Sciences
- R35GM145239
- Caltech groups
- Division of Chemistry and Chemical Engineering (CCE)
- Publication Status
- Submitted