ZACA reaction

From Wikipedia, the free encyclopedia
Jump to: navigation, search
ZACA reaction
Reaction type transition metal catalyzed organometallic functionalization
organoaluminum compound
chiralzirconium catalyst
oxygen (optional)
chiral alcohol
aluminum oxide
Typical solvents typically DCM

The zirconium-catalyzed asymmetric carbo-alumination reaction (or ZACA 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-indenylzirconium 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 organoaluminium 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[edit]


  1. ^ Ei-ichi Negishi, ARKIVOC, 2011 (viii) 34-53, and references therein.
  2. ^ Denis Y. Kondakov; Ei-ichi Negishi (1995). J. Am. Chem. Soc. 117 (43): 10771–10772. doi:10.1021/ja00148a031.  Missing or empty |title= (help)
  3. ^ Bo Liang (2007). Zirconium-catalyzed Asymmetric Carboalumination of Alkenes (ZACA reaction): Its development and application to the synthesis of deoxypolypropionates and other chiral compounds (Google Books excerpt) (Ph.D. thesis). Perdue University. p. 29. ISBN 978-0-549-50694-2. 
  4. ^ Ze Tan; Bo Liang; Shouquan Huo; Ji-cheng Shi; Ei-ichi Negishi (2006). Tetrahedron: Asymmetry. 17 (4): 512–515. doi:10.1016/j.tetasy.2006.01.017.  Missing or empty |title= (help)