Title
Studies on syntheses of polyfunctionalized heteroarenes by
transition metal catalyses( 内容の要旨(Summary) )
Author(s)
山口, 英士
Report No.(Doctoral
Degree)
博士(工学) 甲第401号
Issue Date
2011-03-25
Type
博士論文
Version
publisher
URL
http://hdl.handle.net/20.500.12099/36584
※この資料の著作権は、各資料の著者・学協会・出版社等に帰属します。
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