1,2-Addition or Enolization? Variable Reactivity of a Cerium Acetylide Complex toward Carbonyl Compounds

被引：11

作者：

Kim, Jee Eon ^{[1
]}

Zabula, Alexander V. ^{[1
]}

Carroll, Patrick J. ^{[1
]}

Schelter, Eric J. ^{[1
]}

机构：

[1] Univ Penn, Dept Chem, P Roy & Diana T Vagelos Labs, 231 South 34th St, Philadelphia, PA 19104 USA

来源：

ORGANOMETALLICS | 2016年 / 35卷 / 12期

基金：

美国国家科学基金会;

关键词：

ORGANOMAGNESIUM REAGENTS; NUCLEOPHILIC-ADDITION; GRIGNARD-REAGENTS; CHLORIDE; KETONES; GENERATION; ACIDITIES; STABILITY; CHEMISTRY; ARYLOXIDE;

D O I：

10.1021/acs.organomet.6b00290

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The reactions of the cerium alkyne complex bearing 2,6-bis(dimethylamino)-4-methylphenolate supporting ligands (bdmmp) and a terminal acetylide moiety, Na[Ce(C CPh)(bdmmp)(3)] (1), with benzaldehyde and a family of enolizable ketones led to different products depending on the acidity of the parent carbonyl compound. The reactions of 1 with benzaldehyde, acetone, benzylideneacetone, or 1,1-diphenylacetone (pK(a)(DMSO) = 26.5-19.4) gave the products of nucleophilic addition of type Na[Ce(O-CR2-C CPh)-(bdmmp)(3)] featuring a new C-C bond. In contrast, the reaction of 1 with beta-tetralone (pK(a)(DMSO) = 17.6) resulted in the enolization and deprotonation of beta-tetralone with subsequent replacement of the acetylide ligand at the cerium ion by the enolate. Molecular structures for the cerium products were determined by X-ray diffraction studies, providing valuable information about the performance of organocerium reagents.

引用

页码：2086 / 2091

页数：6

共 50 条

[1] Synthesis, Structural Characterization, and Carbonyl Addition Reactivity of a Terminal Cerium(III) Acetylide Complex
Kim, Jee Eon
Weinberger, David S.
Carroll, Patrick J.
Schelter, Eric J.
[J]. ORGANOMETALLICS, 2014, 33 (21) : 5948 - 5951
[2] 1,2-ADDITION AND 1,4-ADDITION IN THE REACTIONS OF CARBONYL-COMPOUNDS WITH 1,3-BUTADIENE INDUCED BY CERIUM(IV) AMMONIUM-NITRATE
BACIOCCHI, E
RUZZICONI, R
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1986, 51 (10): : 1645 - 1649
[3] ME3SICL-ASSISTED 1,2-ADDITION OF ORGANOCUPRATES TO CARBONYL-COMPOUNDS
MATSUZAWA, S
ISAKA, M
NAKAMURA, E
KUWAJIMA, I
[J]. TETRAHEDRON LETTERS, 1989, 30 (15) : 1975 - 1978
[4] In/InCl3-mediated 1,2-addition of allyl group to α,β-unsaturated carbonyl compounds
Kim, HY
Choi, KI
Pae, AN
Koh, HY
Choi, JH
Cho, YS
[J]. SYNTHETIC COMMUNICATIONS, 2003, 33 (11) : 1899 - 1904
[5] Copper-Catalyzed 1,2-Addition of α-Carbonyl Iodides to Alkynes
Xu, Tao
Hu, Xile
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2015, 54 (04) : 1307 - 1311
[6] Nontrigonal constraint enhances 1,2-addition reactivity of phosphazenes
Lin, Yi-Chun
Gilhula, James C.
Radosevich, Alexander T.
[J]. CHEMICAL SCIENCE, 2018, 9 (18) : 4338 - 4347
[7] Metal or ammonium alginates as Lewis base catalysts for the 1,2-addition of silyl nucleophiles to carbonyl compounds
Verrier, Cecile
Oudeyer, Sylvain
Dez, Isabelle
Levacher, Vincent
[J]. TETRAHEDRON LETTERS, 2012, 53 (15) : 1958 - 1960
[8] Bulky N-Heterocyclic-Carbene-Coordinated Palladium Catalysts for 1,2-Addition of Arylboron Compounds to Carbonyl Compounds
Okuda, Yuta
Nagaoka, Masahiro
Yamamoto, Tetsuya
[J]. CHEMCATCHEM, 2020, 12 (24) : 6291 - 6300
[9] QUESTION OF 1,2-ADDITION OR 1,4-ADDITION OF ORGANOLITHIUM COMPOUNDS TO QUINOLINES
CRAWFORTH, CE
METHCOHN, O
RUSSELL, CA
[J]. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1972, (22): : 2807 - 2810
[10] SELECTIVE 1,2-ADDITION OF ORGANOCERIUM(III) REAGENTS TO ALPHA,BETA-UNSATURATED CARBONYL-COMPOUNDS
IMAMOTO, T
SUGIURA, Y
[J]. JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, 1989, 2 (02) : 93 - 102

← 1 2 3 4 5 →