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N‐Functionalized Ferrocenes: Subvalent Group XIV Element Chlorides and tert ‐Butyllithium‐Induced C−C Bond Cleavage under Mild Conditions
Author(s) -
Nayyar Bastian,
Alnasr Hazem,
Hiller Wolf,
Jurkschat Klaus
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201800128
Subject(s) - chemistry , amide , stereocenter , medicinal chemistry , bond cleavage , butyllithium , stereochemistry , ferrocene , ligand (biochemistry) , main group element , carbon group , derivative (finance) , cleavage (geology) , metalation , metal , transition metal , group (periodic table) , organic chemistry , catalysis , receptor , enantioselective synthesis , biochemistry , electrode , electrochemistry , geotechnical engineering , fracture (geology) , financial economics , engineering , economics
The ferrocene derivative (η 5 ‐Cp)Fe{η 5 ‐C 5 H 3 ‐1‐(ArNCH)‐2‐(CH 2 NMe 2 )} ( 1 ; Ar=2,6‐iPr 2 C 6 H 3 )) reacts diastereoselectively with LiR by carbolithiation and subsequent hydrolysis to give (η 5 ‐Cp)Fe{η 5 ‐C 5 H 3 ‐1‐(ArHNCHR)‐2‐(CH 2 NMe 2 )} ( 3 : R=tBu; 4 : R=Ph; 5 : R=Me) in high yields. For R=tBu, the organolithium derivative (η 5 ‐Cp)Fe{η 5 ‐C 5 H 3 ‐1‐(ArLiNCHR)‐2‐(CH 2 NMe 2 )} ( 2 ) was isolated. Compound 2 reacts with GeCl 2 ⋅dioxane and SnCl 2 to give the metallylene amide chlorides (η 5 ‐Cp)Fe{η 5 ‐C 5 H 3 ‐1‐(ArMNCHtBu)‐2‐(CH 2 NMe 2 )} 6 (M=GeCl) and 7 (M=SnCl), respectively, which each contain three stereogenic centers. The potential of 7 as a ligand in transition‐metal chemistry is demonstrated by formation of its complex (η 5 ‐Cp)Fe{η 5 ‐C 5 H 3 ‐1‐(ArMNCHtBu)‐2‐(CH 2 NMe 2 )} [ 9 , M= Sn(Cl)W(CO) 5 ]. Treatment of 3 with tert‐butyllithium at room temperature causes an unprecedented carbon–carbon bond cleavage whereas under kinetic control, lithiation at the Cp‐3 position takes place, which leads to the isolation of (η 5 ‐Cp)Fe{η 5 ‐C 5 H 3 ‐1‐(ArHNCHtBu)‐2‐(CH 2 NMe 2 )‐3‐SiMe 3 } ( 10 ).