Diastereoselective Synthesis of Polysubstituted 2‐Amidino Thiolanes via Cycloaddition of N ‐Thioacyl Amidines With Donor–Acceptor Cyclopropanes
Abstract
A MgBr 2 ‐catalyzed (3 + 2) cycloaddition between N ‐thioacyl amidines and donor–acceptor cyclopropanes (DACs) has been developed, enabling the highly diastereoselective synthesis of polysubstituted 2‐amidino‐thiolanes in up to 92% yield and with dr values exceeding 99:1. The reaction proceeds under mild conditions and tolerates a broad range of DACs. The structures and relative configurations of the major diastereomers were established by single‐crystal X‐ray diffraction analysis of two representative derivatives. Further derivatization, including sulfur oxidation and an unexpected decarboxylative rearrangement to dihydrothiophenes, highlights the synthetic versatility of the products. DFT calculations suggest that the high diastereoselectivity arises from a lower‐energy cyclization transition state leading to the cis isomer. This work provides efficient access to sulfur‐containing heterocycles bearing the valuable amidine functionality.
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BibTeX
@article{tual2026diastereoselective,
title = {{Diastereoselective Synthesis of Polysubstituted 2‐Amidino Thiolanes via Cycloaddition of N ‐Thioacyl Amidines With Donor–Acceptor Cyclopropanes}},
author = {Laurine Tual and Thomas Cherioux and Romain Pertschi and Gaëlle Blond and Mihaela Gulea},
journal = {Advanced Synthesis and Catalysis},
year = {2026},
month = aug,
doi = {10.1002/adsc.70712},
url = {https://hal.science/hal-05722900v1},
note = {CC BY-SA 4.0},
}
RIS
TY - JOUR
TI - Diastereoselective Synthesis of Polysubstituted 2‐Amidino Thiolanes via Cycloaddition of N ‐Thioacyl Amidines With Donor–Acceptor Cyclopropanes
AU - Laurine Tual
AU - Thomas Cherioux
AU - Romain Pertschi
AU - Gaëlle Blond
AU - Mihaela Gulea
PY - 2026
DA - 2026/08/13
JO - Advanced Synthesis and Catalysis
DO - 10.1002/adsc.70712
UR - https://hal.science/hal-05722900v1
AB - A MgBr 2 ‐catalyzed (3 + 2) cycloaddition between N ‐thioacyl amidines and donor–acceptor cyclopropanes (DACs) has been developed, enabling the highly diastereoselective synthesis of polysubstituted 2‐amidino‐thiolanes in up to 92% yield and with dr values exceeding 99:1. The reaction proceeds under mild conditions and tolerates a broad range of DACs. The structures and relative configurations of the major diastereomers were established by single‐crystal X‐ray diffraction analysis of two representative derivatives. Further derivatization, including sulfur oxidation and an unexpected decarboxylative rearrangement to dihydrothiophenes, highlights the synthetic versatility of the products. DFT calculations suggest that the high diastereoselectivity arises from a lower‐energy cyclization transition state leading to the cis isomer. This work provides efficient access to sulfur‐containing heterocycles bearing the valuable amidine functionality.
SN - 1615-4150
SN - 1615-4169
ER -