{{context|date=March 2017}} {{technical|date=July 2025}} {{Reactionbox | verifiedrevid = | Reference = | Type = transition metal catalyzed organometallic functionalization | Section1 = {{Reactionbox Conditions | Solvent = typically DCM }} | Reaction = {{Reactionbox Reaction | Reactant1 = alkene | Reactant2 = organoaluminum compound | Reactant3 = chiral zirconium catalyst | Reactant4 = oxygen (optional) | Product1 = chiral alcohol | Sideproduct1 = aluminum oxide }} }} The '''zirconium-catalyzed asymmetric carbo-alumination reaction''' (or '''ZACA reaction''') was developed by Nobel laureate Ei-ichi Negishi.<ref name=discovery>{{cite journal |last1=Negishi |first1=Ei-ichi |authorlink1= Ei-ichi Negishi |journal=Arkivoc |title=Discovery of ZACA reaction − Zr-catalyzed asymmetric carboalumination of alkenes |date=2010 |volume=2011 |issue=8 |page=34-45 |doi=10.3998/ark.5550190.0012.803 |publisher=Arkat USA|url=http://www.arkat-usa.org/get-file/37396/|doi-access=free |hdl=2027/spo.5550190.0012.803 |hdl-access=free }}</ref> It facilitates the chiral functionalization of alkenes using organoaluminium compounds under the influence of chiral bis-indenylzirconium catalysts [https://pubs.acs.org/doi/10.1021/acs.accounts.6b00338](e.g. bearing chiral terpene residues,<ref name=konda>{{cite journal | author1 = Denis Y. Kondakov | author2 = Ei-ichi Negishi | authorlink2 = Ei-ichi Negishi | title=Zirconium-catalyzed enantioselective methylalumination of monosubstituted alkenes | journal = J. Am. Chem. Soc. | year = 1995 | volume = 117 | issue = 43 | pages = 10771–10772 | doi = 10.1021/ja00148a031 | bibcode = 1995JAChS.11710771K }}</ref> as in (+)- or (−)-bis[(1-neomenthyl)indenyl]zirconium dichloride<ref name=Liang>{{cite thesis | degree = Ph.D. | author = Bo Liang | title = Zirconium-catalyzed Asymmetric Carboalumination of Alkenes (ZACA reaction): Its development and application to the synthesis of deoxypolypropionates and other chiral compounds| pages = 29 | format = Google Books excerpt | url = https://books.google.com/books?id=5_kYT5nOuq8C&pg=PA29 | publisher = Purdue University | year = 2007 | isbn = 978-0-549-50694-2 }}</ref><ref>{{cite journal |last1=Xu |first1=Shiqing |last2=Oda |first2=Akimichi |last3=Kamada |first3=Hirofumi |last4=Negishi |first4=Ei-ichi |authorlink4=Ei-ichi Negishi |title=Highly enantioselective synthesis of γ-, δ-, and ε-chiral 1-alkanols via Zr-catalyzed asymmetric carboalumination of alkenes (ZACA)–Cu- or Pd-catalyzed cross-coupling |journal=Proceedings of the National Academy of Sciences of the United States |date=2014-06-10 |volume=111 |issue=23 |pages=8368–8373 |doi=10.1073/pnas.1401187111 |publisher=National Academy of Sciences |jstor=23776425 |pmid=24912191 |pmc=4060698 |doi-access=free }}</ref>). 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.
== See also == *Organoaluminium chemistry *Organozirconium chemistry *Indenyl effect
== References == {{Reflist}}
{{reaction-stub}} Category:Organometallic chemistry Category:Catalysis