62116-24-9Relevant academic research and scientific papers
Second-coordination sphere effects on the reactivities of Hoveyda-Grubbs-type catalysts: A ligand exchange study using phenolic moiety-functionalized ligands
Akiyama, Naoki,Goshima, Kenta,Hirota, Shun,Jatmika, Catur,Matsuo, Takashi,Wakabayashi, Kazumo
supporting information, p. 11618 - 11627 (2020/09/09)
The Hoveyda-Grubbs (HG) second-generation catalyst (HG-II), a Ru complex with a 2-isopropoxybenzylidene ligand, is extensively used for olefin metathesis, the rearrangement of carbon-carbon double bonds. A well-known strategy to control its complex reactivity is to modify the phenyl ring in the ligand, thereby directly influencing the coordination of the phenolic oxygen to the metal center. We, herein, report that a functional group attached to the phenolic moiety in the 2-alkoxybenzylidene ligand can indirectly affect the reactivities of HG-type complexes. In this work, the ligand exchange reactions between HG-II and phenolic moiety-modified 2-alkoxybenzylidene ligands are useful for evaluating the structural effects of the ligands. Specifically, an ethylene amide or an ester group at the terminal phenolic moiety in the benzylidene ligand was found to influence the relative stabilities of HG-type complexes compared to that of the HG-II complex. The structural analyses proved that the observed effects of the functional groups on the complex stabilities originate from the interactions with a chlorido ligand in HG-type complexes without changes in coordination fashions at the metal centers. It was found that the outer-sphere interactions also influence the catalytic activities of HG-type complexes, namely, the properties of HG-type complexes can be controlled by outer-sphere structural factors toward the metal center (i.e., "the second-coordination sphere effect"). In the design of functionalized HG-type complexes, the outer-sphere structural effects need to be considered in addition to the optimization of the metal coordination site.
Synthetic utility of stannyl enolates as radical alkylating agents
Miura, Katsukiyo,Fujisawa, Naoki,Saito, Hiroshi,Wang, Di,Hosomi, Akira
, p. 2591 - 2594 (2007/10/03)
(Equation presented) The radical-initiated β-ketoalkylation of haloalkanes with tributylstannyl enolates is described. Stannyl enolates derived from aromatic ketones are reactive toward the homolytic β-ketoalkylation of simple haloalkanes as well as those activated by an electron-withdrawing group. The reactivity of stannyl enolates as radical alkylating agents can be utilized for an efficient three-component coupling reaction among stannyl enolates, haloalkanes, and electron-deficient alkenes.
Indocarbocyanine and benzindocarbocyanine phosphoramidites
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, (2008/06/13)
A chemical compound of the following formula is disclosed: STR1 where R is selected from the group consisting of H, trityl, 4-O-monomethoxytrityl, 4,4'-O-dimethoxytrityl, and acyl groups, and whereby R can be used as a protecting group or is an H; R' is a phosphoramidite; R" is selected from the group consisting of H and lower alkyl groups; R'" is selected from the group consisting of H and lower alkyl groups; R4 is selected from the group consisting of H, lower alkyl, acyl, STR2 and (CH2)p COO(CH2)q CH3 wherein p is an integer from 0 to 4 and q is an integer from 0 to 4; R5 is selected from the group consisting of H, lower alkyl, acyl, STR3 and (CH2)p COO(CH2)q CH3 wherein p is an integer from 0 to 4 and q is an integer from 0 to 4; n is an integer from 0 to 10; m is an integer from 0 to 10; r is 1, 2, or 3; and X- is a negative ion.
Indocarbocyanine-linked phosphoramidites
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, (2008/06/13)
A chemical compound of the following formula is disclosed STR1 where R is one of H, trityl, 4-0-monomethoxytrityl, 4,4'-O-dimethoxytrityl, or acyl groups and R may be used as a protecting group or is an H; R1 is a phosphoramidite; R11 is one of H or lower alkyl groups; R111 is one of H or lower alkyl groups; R4 is one of H, lower alkyl, acyl, or (CH2)p COO(CH2)q CH3 where p is an integer from 0 to 4 and q is an integer from 0 to 4; R5 is one of H, lower alkyl, acyl, or (CH2)p COO(CH2)q CH3 where p is an integer from 0 to 4 and q is an integer from 0 to 4; n is an integer from 0 to 10; m is an integer from 0 to 10; and r is 1, 2, or 3.
NOVEL USE OF ORGANOTIN HALIDE-BASE COMPLEX IN ORGANIC SYNTHESIS. CYCLOADDITION REACTION OF OXETANE WITH ISOCYANATES.
Baba, Akio,Shibata, Ikuya,Fujiwara, Masahiro,Matsuda, Haruo
, p. 5167 - 5170 (2007/10/02)
Cycloadditions of oxetanes with isocyanates were markedly accelerated by the complex of Bu2SnI2 and Ph3P=O which could be readily handled and hardly caused a trimerization of isocyanates, yielding oxazin-2-ones under neutral and mild reaction conditions.
