ZACA reaction
| ZACA reaction | |||||||||||||||
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| Reaction type | transition metal catalyzed organometallic functionalization | ||||||||||||||
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| Typical solvents | typically DCM | ||||||||||||||
The Zirkonium-catalyzed Asymmetric Carbo-Alumination reaction was developed by Nobel laureate Ei-ichi Negishi.[1] It facilitates the chiral functionalization of alkenes using organoaluminium compounds under the influence of chiral bis-indenylzirkonium catalysts (e.g. bearing chiral terpene residues,[2] as in (+)- or (-)-bis[(1-neomenthyl)indenyl]zirconium dichloride[3]). In a first step the alkene inserts into an Al-C bond of the reagent, forming a new chiral organoaluminum compound in which the aluminium atom occupies the lesser hindered position. This intermediate is usually oxidized by oxygen to form the corresponding chiral alcohol (cf. Hydroboration–oxidation reaction). The reaction can also be applied to dienes, where the least sterically hindered double bond is attacked selectively.[4]
See also
References
- ^ Ei-ichi Negishi, ARKIVOC, 2011 (viii) 34-53, http://www.arkat-usa.org/get-file/37396/ and references therein.
- ^ Denis Y. Kondakov, Ei-ichi Negishi, J. Am. Chem. Soc., 1995, 117 (43), pp 10771–10772, doi:10.1021/ja00148a031
- ^ http://books.google.de/books?id=5_kYT5nOuq8C&pg=PA29&lpg=PA29&dq=neomenthylindene&source=bl&ots=kSaXQtg_bL&sig=T_MBdxCN_B5B3ccataPAlYyC_08&hl=de&ei=9lKOTqSuIuqL0AWnuMUY&sa=X&oi=book_result&ct=result&resnum=4&ved=0CC4Q6AEwAw#v=onepage&q=neomenthylindene&f=false
- ^ Ze Tan, Bo Liang, Shouquan Huo, Ji-cheng Shi, Ei-ichi Negishi, Tetrahedron: Asymmetry Volume 17, Issue 4, 20 February 2006, Pages 512-515, doi:10.1016/j.tetasy.2006.01.017.