Ni-Pd Catalyzed Cyclization of Sulfanyl 1,6-Diynes: Synthesis of 1'-Homonucleoside Analogues

Yuka Kobayashi; Rena Tanahashi; Yui Yamaguchi; Noriyuki Hatae; Masanori Kobayashi; Yoshihito Ueno; Mitsuhiro Yoshimatsu

doi:10.1021/acs.joc.6b02841

Ni-Pd Catalyzed Cyclization of Sulfanyl 1,6-Diynes: Synthesis of 1'-Homonucleoside Analogues

J Org Chem. 2017 Mar 3;82(5):2436-2449. doi: 10.1021/acs.joc.6b02841. Epub 2017 Feb 15.

Authors

Yuka Kobayashi¹, Rena Tanahashi¹, Yui Yamaguchi², Noriyuki Hatae³, Masanori Kobayashi⁴, Yoshihito Ueno⁵, Mitsuhiro Yoshimatsu^{1

2}

Affiliations

¹ Department of Chemistry, Faculty of Education, Gifu University , Yanagido 1-1, Gifu 501-1193, Japan.
² Laboratory of Veterinary Microbiology, Faculty of Applied Biological Sciences, Gifu University , Yanagido 1-1, Gifu 501-1193, Japan.
³ School of Pharmaceutical Sciences, Health Science University of Hokkaido , Ishikari-Tobetsu, Hokkaido 061-0293, Japan.
⁴ Organization for Research and Community Development, Department of Research Promotion, Gifu University , Yanagido 1-1, Gifu 501-1193, Japan.
⁵ Department of Smart Material Science, The United Graduate School of Agricultural Science, Gifu University , Yanagido 1-1, Gifu 501-1193, Japan.

PMID: 28151664
DOI: 10.1021/acs.joc.6b02841

Abstract

The Ni-Pd catalyzed addition-cyclization of sulfanyl 1,6-diynes 2-9 with nucleobases is described. The reactions of N-tethered 1,6-diynes with N³-benzoylthymine, N⁴,N⁴-bis(Boc)cytosine, N³-benzoyluracil and N⁶,N⁶-bis(Boc)adenine exclusively afforded the pyrrolylmethyl and furylmethyl nucleotides in good yields. Deprotection of nucleobases was completed by treatment with acids or bases. Furthermore, the reactions of pyrroles and furans with nucleophiles such as alkoxides and amines underwent detosylation and conversion to the alkoxymethyl- and arylaminomethyl-pyrroles and furans in good yields.