# Stereoselective Alkene Carbofunctionalization: Method Development and Mechanism

> **NIH NIH R01** · NEW YORK UNIVERSITY · 2020 · $463,824

## Abstract

Project Summary
 The goal of this research program is to develop stereoselective and regioselective alkene
carbofunctionalization methods to enable efficient and sustainable organic syntheses. A major
challenge in pharmaceutical synthesis is the catalytic construction of chiral molecules. Alkenes
are versatile functional groups. 1,2-Dicarbofunctionalization and hydroalkylation of alkenes have
emerged as compelling strategies to rapidly increase molecular complexity, but intermolecular
asymmetric methods have not yet been developed for simple alkenes. The research projects
described in this proposal address these synthetic challenges by developing a series of
enantioselective reductive 1,2-dicarbofunctionalization and branch-selective hydroalkylation
reactions of a broad scope of alkenes. These new methods would enable efficient routes to
access target molecules with complex substitution patterns while introducing stereocenters.
Catalyst development is built on the hypothesis that Ni-mediated radical addition to alkenes could
result in new stereo-determining steps, such as radical capture or reductive elimination.
Systematic mechanistic studies will be carried out to build stereochemical models, and insight
gained will help overcome the limitations encountered in expanding the scope and utility of the
new methods. Preliminary results showing new reactivity and verifying mechanistic proposals
provide compelling evidence for the feasibility of this research. The expected outcomes of this
research are as follows: (1) The development of stereoselective and regioselective reductive
carbofunctionalization reactions of alkenes will allow for efficient access to vicinal disubstitution
patterns and tertiary carbon centers, and thus novel retrosynthetic disconnections of
pharmaceutical molecules; (2) The insight gained from mechanistic studies of model reactions
and catalysts will not only facilitate the rational design of catalysts for the reactions described in
this proposal, but also provide a guideline for understanding Ni-catalyzed coupling reactions more
broadly.

## Key facts

- **NIH application ID:** 9896861
- **Project number:** 5R01GM127778-02
- **Recipient organization:** NEW YORK UNIVERSITY
- **Principal Investigator:** Tianning Diao
- **Activity code:** R01 (R01, R21, SBIR, etc.)
- **Funding institute:** NIH
- **Fiscal year:** 2020
- **Award amount:** $463,824
- **Award type:** 5
- **Project period:** 2019-04-01 → 2024-03-31

## Primary source

NIH RePORTER: https://reporter.nih.gov/project-details/9896861

## Citation

> US National Institutes of Health, RePORTER application 9896861, Stereoselective Alkene Carbofunctionalization: Method Development and Mechanism (5R01GM127778-02). Retrieved via AI Analytics 2026-05-23 from https://api.ai-analytics.org/grant/nih/9896861. Licensed CC0.

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