The nitrogen-interrupted Nazarov cyclization can be a powerful method for the stereocontrolled synthesis of sp 3 -rich N -heterocycles. However, due to the incompatibility between the basicity of nitrogen and the acidic reaction conditions, examples of this type of Nazarov cyclization are scarce. Herein, we report a one-pot nitrogen-interrupted halo -Prins/ halo -Nazarov coupling cascade that joins two simple building blocks, an enyne and a carbonyl partner, to furnish functionalized cyclopenta[ b ]indolines with up to four contiguous stereocenters. For the first time, we provide a general method for the alkynyl halo -Prins reaction of ketones, thus enabling the formation of quaternary stereocenters. Additionally, we describe the outcomes of secondary alcohol enyne couplings, which exhibit helical chirality transfer. Furthermore, we investigate the impact of aniline enyne substituents on the reaction and evaluate the tolerance of different functional groups. Finally, we discuss the reaction mechanism and demonstrate various transformations of the prepared indoline scaffolds, highlighting their applicability in drug discovery campaigns.
more »
« less
This content will become publicly available on July 2, 2026
Quaternary Carbon as a Locus for Skeletal Disconnection. Total Synthesis of (±)-Tubingensin A Featuring Assembly of the Backbone Stereotriad Using a Halo -Prins/ Halo -Nazarov Cascade
- Award ID(s):
- 2215973
- PAR ID:
- 10653905
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- Journal of the American Chemical Society
- Volume:
- 147
- Issue:
- 26
- ISSN:
- 0002-7863
- Page Range / eLocation ID:
- 23120 to 23127
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Precise and accurate predictions of the halo mass function for cluster mass scales inwνCDM cosmologies are crucial for extracting robust and unbiased cosmological information from upcoming galaxy cluster surveys.Here, we present a halo mass function emulator for cluster mass scales (≳ 1013M⊙/h) up to redshiftz= 2 with comprehensive support for the parameter space ofwνCDM cosmologies allowed by current data.Based on theAemulusνsuite of simulations, the emulator marks a significant improvement in the precision of halo mass function predictions by incorporating both massive neutrinos and non-standard dark energy equation of state models.This allows for accurate modeling of the cosmology dependence in large-scale structure and galaxy cluster studies.We show that the emulator, designed using Gaussian Process Regression, has negligible theoretical uncertainties compared to dominant sources of error in future cluster abundance studies.Our emulator is publicly available (https://github.com/DelonShen/aemulusnu_hmf), providing the community with a crucial tool for upcoming cosmological surveys such as LSST and Euclid.more » « less
An official website of the United States government
