# Expanding the Synthetic Utility of β-Keto Esters in Enantioconvergent Addition Reactions and Progress Towards a Convergent, De Novo Synthesis of Jervine

> **NIH NIH F31** · UNIV OF NORTH CAROLINA CHAPEL HILL · 2021 · $37,516

## Abstract

Project Summary
The need for efficient methods to construct chiral building blocks has been increasing significantly
over the last 20 years because of the implementation of regulatory guidelines regarding the
creation of new stereodefined drugs. While hydrogenative transformations of β-keto esters are
well established and used extensively in industry to provide over 100 tons of material annually,
asymmetric and chemoselective transformations with γ,δ-unsaturated β-ketoesters remain
underexplored due to their diverse functionality and unconventional electronic biases. This
proposal aims to develop practical catalytic reactions that take advantage of the high tunability of
ligated copper species to selectively functionalize one of the three possible electrophilic sites in
these molecules chemo- and stereoselectively. These methods will provide access to highly
diversifiable enantioenriched secondary and tertiary allylic alcohols containing two contiguous
stereocenter and a carboxylate moiety, and will expand the synthetic utility of β-dicarbonyl
compounds by exploiting their potential electrophilicity towards other nucleophiles. Aligning with
our interest in accessing structurally complex and biologically relevant natural products, we are
proposing a tunable and convergent approach that will provide access to unnatural variants of the
Veratrum alkaloid jervine. Our strategy involves a diastereoselective conjugate addition of a
complex steroid fragment with a stereochemically dense alkaloidal tricycle.

## Key facts

- **NIH application ID:** 10225321
- **Project number:** 5F31GM137607-02
- **Recipient organization:** UNIV OF NORTH CAROLINA CHAPEL HILL
- **Principal Investigator:** Pedro R De Jesús Cruz
- **Activity code:** F31 (R01, R21, SBIR, etc.)
- **Funding institute:** NIH
- **Fiscal year:** 2021
- **Award amount:** $37,516
- **Award type:** 5
- **Project period:** 2020-08-01 → 2022-07-31

## Primary source

NIH RePORTER: https://reporter.nih.gov/project-details/10225321

## Citation

> US National Institutes of Health, RePORTER application 10225321, Expanding the Synthetic Utility of β-Keto Esters in Enantioconvergent Addition Reactions and Progress Towards a Convergent, De Novo Synthesis of Jervine (5F31GM137607-02). Retrieved via AI Analytics 2026-05-24 from https://api.ai-analytics.org/grant/nih/10225321. Licensed CC0.

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