# The Pd-catalyzed intermolecular enantioselective aza-Heck reaction

> **NIH NIH F32** · UTAH STATE HIGHER EDUCATION SYSTEM--UNIVERSITY OF UTAH · 2020 · $65,310

## Abstract

Project Summary
 The ability to construct C–N bonds enantioselectively through a catalytic intermolecular process with
simple robust methods remains a standing challenge in the field of transition metal catalysis. In particular, the
development of the addition of amines and other nucleophiles to unactivated internal alkenes has proven to be
especially challenging. Preliminary studies in the Sigman group have recently uncovered conditions to
accomplish the first example of a Pd-catalyzed intermolecular enantioselective addition of amines to
unactivated allylic alcohols through the use of the redox-relay Heck reaction strategy. A primary goal of this
proposal is to understand the factors that govern this exciting new transformation so that it can be extended to
a broader range of N–H nucleophiles and more challenging alkenes. To accomplish this, I will address a series
of mechanistic questions to better understand the factors that are critical to the success of the reaction. Firstly,
I will synthesize a systematic library of substrates and submit them to the reaction in order to develop
quantitative structure activity relationships. With this data, predictive models will be determined through the use
of correlation techniques that the Sigman group has recently developed. In addition, I will undertake
mechanistic studies to determine whether the key aminopalladation event occurs through a syn- or anti-
pathway, a factor that significantly effects the development and application of this methodology. On the basis
of these experiments, I plan to extend this methodology to more highly substituted N–H nucleophiles (such as
primary amides and carbamates) and a broader range of alkenes. The ability to convert achiral amines and
alkenes to enantiopure chiral amines is a significant advancement that will allow the rapid generation of some
of the most commonly encountered structural motifs found in natural products and chiral drugs.

## Key facts

- **NIH application ID:** 9857477
- **Project number:** 5F32GM128354-02
- **Recipient organization:** UTAH STATE HIGHER EDUCATION SYSTEM--UNIVERSITY OF UTAH
- **Principal Investigator:** Sean P Ross
- **Activity code:** F32 (R01, R21, SBIR, etc.)
- **Funding institute:** NIH
- **Fiscal year:** 2020
- **Award amount:** $65,310
- **Award type:** 5
- **Project period:** 2019-02-15 → 2021-06-14

## Primary source

NIH RePORTER: https://reporter.nih.gov/project-details/9857477

## Citation

> US National Institutes of Health, RePORTER application 9857477, The Pd-catalyzed intermolecular enantioselective aza-Heck reaction (5F32GM128354-02). Retrieved via AI Analytics 2026-05-23 from https://api.ai-analytics.org/grant/nih/9857477. Licensed CC0.

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