Rhodium-Catalyzed Stereoselective Access to Polysubstituted Bicyclo[1.1.0]butanes Bearing Quaternary Bridge Carbons
- 1Instituto de Investigación Química “Andrés, Universidad de Alcalá, Ctra., Alcalá de Henares, Spain, 28805
Abstract
Bicyclo[1.1.0]butanes (BCBs) are unique strained carbocycles that have emerged as attractive buildingblocks in synthetic and medicinal chemistry owing to their unique reactivity. Despite recent advances in the preparation of polysubstituted BCBs, the stereoselective synthesis of bridge-substituted derivatives remains a significant challenge, particularly when quaternary stereocenters are involved at these positions. Herein, we report a rhodium-catalyzed [2+1] cycloaddition of cyclopropenes and diazo compounds that provides direct access to stereodefined bridge-substituted BCBs. The reaction proceeds with complete diastereocontrol across a broad range of substrates and enables the construction of densely functionalized frameworks bearing up to four stereocenters. The methodology can also be extended to enantioenriched cyclopropenes, providing optically active BCBs with complete enantiospecificity. DFT calculations are consistent with the stereochemical outcome and the synthetic utility of the resulting BCBs is demonstrated by transformations leading to fused tricyclic architectures and polysubstituted cyclobutenes and cyclobutanes.
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BibTeX
@misc{moralesortega2026rhodiumcatalyzed,
title = {{Rhodium-Catalyzed Stereoselective Access to Polysubstituted Bicyclo[1.1.0]butanes Bearing Quaternary Bridge Carbons}},
author = {Guillermo Morales-Ortega and Estíbaliz Merino and R. Martín Romero and Javier Carreras},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008902/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008902/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Rhodium-Catalyzed Stereoselective Access to Polysubstituted Bicyclo[1.1.0]butanes Bearing Quaternary Bridge Carbons
AU - Guillermo Morales-Ortega
AU - Estíbaliz Merino
AU - R. Martín Romero
AU - Javier Carreras
PY - 2026
DA - 2026/09/16
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008902/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008902/v1
AB - Bicyclo[1.1.0]butanes (BCBs) are unique strained carbocycles that have emerged as attractive buildingblocks in synthetic and medicinal chemistry owing to their unique reactivity. Despite recent advances in the preparation of polysubstituted BCBs, the stereoselective synthesis of bridge-substituted derivatives remains a significant challenge, particularly when quaternary stereocenters are involved at these positions. Herein, we report a rhodium-catalyzed [2+1] cycloaddition of cyclopropenes and diazo compounds that provides direct access to stereodefined bridge-substituted BCBs. The reaction proceeds with complete diastereocontrol across a broad range of substrates and enables the construction of densely functionalized frameworks bearing up to four stereocenters. The methodology can also be extended to enantioenriched cyclopropenes, providing optically active BCBs with complete enantiospecificity. DFT calculations are consistent with the stereochemical outcome and the synthetic utility of the resulting BCBs is demonstrated by transformations leading to fused tricyclic architectures and polysubstituted cyclobutenes and cyclobutanes.
ER -