Regio- and Stereoselective Hydroamination of Alkynes Using an Ammonia Surrogate: Synthesis of N-Silylenamines as Reactive Synthons

被引：32

作者：

Lui, Erica K. J. ^{[1
]}

Brandt, Jason W. ^{[1
]}

Schafer, Laurel L. ^{[1
]}

机构：

[1] Univ British Columbia, Dept Chem, 2036 Main Mall, Vancouver, BC V6T 1Z1, Canada

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2018年 / 140卷 / 15期

基金：

加拿大自然科学与工程研究理事会;

关键词：

RING-TRANSFORMATION EQUILIBRIUM; SPONGE ALKALOID CERATAMINE; C-H ACTIVATION; INTERMOLECULAR HYDROAMINATION; IMIDO COMPLEXES; REVERSIBLE 1,2-RH-ELIMINATION; CATALYTIC HYDROAMINATION; N; N-BIS(SILYL); ENAMINES; HYDROCARBON ACTIVATION; EFFICIENT SYNTHESIS;

D O I：

10.1021/jacs.7b13783

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

An anti-Markovnikov selective hydroamination of alkynes with N-silylamines to afford N-silylenamines is reported. The reaction is catalyzed by a bis(amidate)bis(amido)Ti(IV) catalyst and is compatible with a variety of terminal and internal alkynes. Stoichiometric mechanistic studies were also performed. This method easily affords interesting N-silylenamine synthons in good to excellent yields and the easily removable silyl protecting group enables the catalytic synthesis of primary amines.

引用

页码：4973 / 4976

页数：4

共 66 条

[1] Ahlbrecht H., 1982, SYNTHESIS-STUTTGART, V1982, P273
[2] RING TRANSFORMATION EQUILIBRIUM (BOND SWITCH) IN THE 5-(2-AMINOVINYL)ISOTHIAZOLE SYSTEM VIA HYPERVALENT SULFURANE - SYNTHESIS, STRUCTURE DETERMINATION, AND KINETIC-STUDY
AKIBA, KY
KASHIWAGI, K
OHYAMA, Y
YAMAMOTO, Y
OHKATA, K
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (09) : 2721 - 2730
[3] Asymmetric Propargylboration of Aldimines and Ketimines with the Borabicyclo[3.3.2]decanes: Novel Entries to Allenyl Carbinamines, Amino Acids, and Their α-Methyl Counterparts
Alicea-Matias, Eyleen
Soderquist, John A.
[J]. ORGANIC LETTERS, 2017, 19 (02) : 336 - 339
[4] Palladium-mediated C-N, C-C, and C-O functionalization of azolopyrimidines: a new total synthesis of variolin B
Baeza, Alejandro
Mendiola, Javier
Burgos, Carolina
Alvarez-Builla, Julio
Vaquero, Juan J.
[J]. TETRAHEDRON LETTERS, 2008, 49 (25) : 4073 - 4077
[5] Selective palladium-catalyzed amination of the heterocyclic core of variolins
Baeza, Alejandro
Burgos, Carolina
Alvarez-Builla, Julio
Vaquero, Juan J.
[J]. TETRAHEDRON LETTERS, 2007, 48 (14) : 2597 - 2601
[6] Application of Selective Palladium-Mediated Functionalization of the Pyrido[3′,2′:4,5]pyrrolo[1,2-c]pyrimidine Heterocyclic System for the Total Synthesis of Variolin B and Deoxyvariolin B
Baeza, Alejandro
Mendiola, Javier
Burgos, Carolina
Alvarez-Builla, Julio
Vaquero, Juan J.
[J]. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2010, 2010 (29) : 5607 - 5618
[7] Selectivities in hydrocarbon activation: Kinetic and thermodynamic investigations of reversible 1,2-RH-elimination from (silox)(2)((Bu3SiNH)-Bu-t)TiR (silox = (Bu3SiO)-Bu-t)
Bennett, JL
Wolczanski, PT
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (44) : 10696 - 10719
[8] Extracting absolute titanium-alkyl and -hydride bond enthalpies from relative D(TiR(H)) in (silox)2(tBu3SiNH)TiR:: electronegativity and ECT models
Bennett, JL
Vaid, TP
Wolczanski, PT
[J]. INORGANICA CHIMICA ACTA, 1998, 270 (1-2) : 414 - 423
[9] ENERGETICS OF C-H BOND ACTIVATION AND ETHYLENE BINDING TO D(0) TRANSIENT (SILOX)(2)TI=NSI(T)BU(3)
BENNETT, JL
WOLCZANSKI, PT
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (05) : 2179 - 2180
[10] Modular, efficient synthesis of asymmetrically substituted piperazine scaffolds as potent calcium channel blockers
Borzenko, Andrey
Pajouhesh, Hassan
Morrison, Jerrie-Lynn
Tringham, Elizabeth
Snutch, Terrance P.
Schafer, Laurel L.
[J]. BIOORGANIC & MEDICINAL CHEMISTRY LETTERS, 2013, 23 (11) : 3257 - 3261

← 1 2 3 4 5 6 7 →