TY - JOUR
T1 - Halogen–sodium exchange enables efficient access to organosodium compounds
AU - Asako, Sobi
AU - Takahashi, Ikko
AU - Nakajima, Hirotaka
AU - Ilies, Laurean
AU - Takai, Kazuhiko
N1 - Funding Information:
We thank Okayama University, RIKEN, and KOBELCO ECO-Solutions CO., Ltd. for financial support. We thank Dr. Zhaomin Hou and Dr. Masanori Takimoto for generously allowing us to use the mass spectrometer. This paper is dedicated to professor Dietmar Seyferth, who passed away on 6 June 2020.
Publisher Copyright:
© 2021, The Author(s).
PY - 2021/12
Y1 - 2021/12
N2 - With sodium being the most abundant alkali metal on Earth, organosodium compounds are an attractive choice for sustainable chemical synthesis. However, organosodium compounds are rarely used—and are overshadowed by organolithium compounds—because of a lack of convenient and efficient preparation methods. Here we report a halogen–sodium exchange method to prepare a large variety of (hetero)aryl- and alkenylsodium compounds including tri- and tetrasodioarenes, many of them previously inaccessible by other methods. The key discovery is the use of a primary and bulky alkylsodium lacking β-hydrogens, which retards undesired reactions, such as Wurtz–Fittig coupling and β-hydrogen elimination, and enables efficient halogen–sodium exchange. The alkylsodium is readily prepared in situ from neopentyl chloride and an easy-to-handle sodium dispersion. We believe that the efficiency, generality, and convenience of the present method will contribute to the widespread use of organosodium in organic synthesis, ultimately contributing to the development of sustainable organic synthesis by rivalling the currently dominant organolithium reagents.
AB - With sodium being the most abundant alkali metal on Earth, organosodium compounds are an attractive choice for sustainable chemical synthesis. However, organosodium compounds are rarely used—and are overshadowed by organolithium compounds—because of a lack of convenient and efficient preparation methods. Here we report a halogen–sodium exchange method to prepare a large variety of (hetero)aryl- and alkenylsodium compounds including tri- and tetrasodioarenes, many of them previously inaccessible by other methods. The key discovery is the use of a primary and bulky alkylsodium lacking β-hydrogens, which retards undesired reactions, such as Wurtz–Fittig coupling and β-hydrogen elimination, and enables efficient halogen–sodium exchange. The alkylsodium is readily prepared in situ from neopentyl chloride and an easy-to-handle sodium dispersion. We believe that the efficiency, generality, and convenience of the present method will contribute to the widespread use of organosodium in organic synthesis, ultimately contributing to the development of sustainable organic synthesis by rivalling the currently dominant organolithium reagents.
UR - http://www.scopus.com/inward/record.url?scp=85106648232&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85106648232&partnerID=8YFLogxK
U2 - 10.1038/s42004-021-00513-2
DO - 10.1038/s42004-021-00513-2
M3 - Article
AN - SCOPUS:85106648232
VL - 4
JO - Communications Chemistry
JF - Communications Chemistry
SN - 2399-3669
IS - 1
M1 - 76
ER -