Cu-Catalyzed Formal Methylative and Hydrogenative Carboxylation of Alkynes with Carbon Dioxide: Efficient Synthesis of α,β-Unsaturated Carboxylic Acids

Carbon dioxide reacts with 2,3-dimethylbutadiene and bis-cyclooctadiene(1,5)-nickel(O) in the presence of N,N′-tetramethyl-ethylendiamine (tmeda) to form [(3,4,5-η3)-3,4-dimethyl-3-pentenylato](N,N′-tetramethyl-ethylendiamine)-nickel(II) as the product of the oxidative coupling of CO2 and the diene. The deep red complex crystallizes in the rhombic space group Pbca. The structure was determined by an X-ray analysis. The monodendate carboxylate group, the π-allyl system and a N-atom of tmeda form a planar coordination sphere around the central atom. The distance between Ni and the second N-atom of tmeda is very long (2.314 Å). Reaction of the complex with R−X (R: H, CH3) yield 3-unsaturated carboxylic acids; tmeda can be substituted by 2,2′-bipyridine.

Download Full-text

Oxidative Cyclization of β,γ-Unsaturated Carboxylic Acids Using Hypervalent Iodine Reagents: An Efficient Synthesis of 4-Substituted Furan-2-ones

Synthesis ◽

10.1055/s-0036-1588987 ◽

2017 ◽

Vol 49 (13) ◽

pp. 2907-2912 ◽

Cited By ~ 3

Author(s):

Kensuke Kiyokawa ◽

Satoshi Minakata ◽

Kenta Takemoto ◽

Shunsuke Yahata ◽

Takumi Kojima

Keyword(s):

Organic Chemistry ◽

Carboxylic Acids ◽

Present Method ◽

Medicinal Chemistry ◽

Oxidative Cyclization ◽

Hypervalent Iodine ◽

Efficient Synthesis ◽

Substitution Pattern ◽

Unsaturated Carboxylic Acids

The oxidative cyclization of β-substituted β,γ-unsaturated carboxylic acids using a hypervalent iodine reagent to provide 4-substituted furan-2-one products, is reported. In this cyclization, the use of a highly electrophilic PhI(OTf)2, which is in situ prepared from PhI(OAc)2 and Me3SiOTf, is crucial. Depending on the substitution pattern at the α-position of the substrates, furan-2(5H)-ones or furan-2(3H)-ones are produced. Thus, the present method offers a useful tool for accessing various types of 4-substituted furan-2-ones that are important structural motifs in the field of organic chemistry and medicinal chemistry.

Download Full-text

AN EFFICIENT SYNTHESIS OF α,β-UNSATURATED CARBOXYLIC ACIDS AND NITRILES

Organic Preparations and Procedures International ◽

10.1080/00304949009356672 ◽

1990 ◽

Vol 22 (1) ◽

pp. 94-97 ◽

Cited By ~ 5

Author(s):

Chang Kiu Lee ◽

Jeung Yeop Shim

Keyword(s):

Carboxylic Acids ◽

Efficient Synthesis ◽

Unsaturated Carboxylic Acids

Download Full-text

Copper-Catalyzed Carboxylation of Alkenylzirconocenes with Carbon Dioxide Leading to α,β-Unsaturated Carboxylic Acids

Organic Letters ◽

10.1021/acs.orglett.5b02619 ◽

2015 ◽

Vol 17 (20) ◽

pp. 5112-5115 ◽

Cited By ~ 31

Author(s):

Sheng Wang ◽

Peng Shao ◽

Chao Chen ◽

Chanjuan Xi

Keyword(s):

Carbon Dioxide ◽

Carboxylic Acids ◽

Unsaturated Carboxylic Acids

Download Full-text

Ni-Catalyzed Carboxylation of Conjugated Dienes with Carbon Dioxide and DIBAL-H for the Synthesis of ß,γ-Unsaturated Carboxylic Acids

Synlett ◽

10.1055/a-1336-8034 ◽

2020 ◽

Author(s):

Masanari Kimura ◽

Ying Luo ◽

Bun Chan ◽

Tsutomu Fukuda ◽

Gen Onodera

Keyword(s):

Carbon Dioxide ◽

Carboxylic Acids ◽

Atmospheric Pressure ◽

Conjugated Dienes ◽

Ni Catalyst ◽

Diisobutylaluminum Hydride ◽

Unsaturated Carboxylic Acids

Ni-catalyst-promoted conjugated dienes undergo 1,2-hydrocarboxylation with carbon dioxide under atmospheric pressure and in the presence of diisobutylaluminum hydride (DIBAL-H). Conjugated dienes react with carbon dioxide in a 1:1 ratio to produce the corresponding β,γ-unsaturated carboxylic acids without suffering from the dimerization or oligomerization of conjugated dienes.

Download Full-text