P[N(i-Bu)CH2CH2]3N: Nonionic Lewis Base for Promoting the Room-Temperature Synthesis of α,β-Unsaturated Esters, Fluorides, Ketones, and Nitriles Using Wadsworth-Emmons Phosphonates

被引：37

作者：

Chintareddy, Venkat Reddy ^{[1
]}

Ellern, Arkady ^{[2
]}

Verkade, John G. ^{[1
]}

机构：

[1] Iowa State Univ, Dept Chem, Ames, IA 50011 USA

[2] Iowa State Univ, Mol Struct Lab, Ames, IA 50011 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2010年 / 75卷 / 21期

基金：

美国国家科学基金会;

关键词：

WITTIG-HORNER REACTION; Z-UNSATURATED ESTERS; HIGHLY STEREOSELECTIVE-SYNTHESIS; CATALYTIC-ACTIVITY RELATIONSHIP; TANDEM REDUCTION-OLEFINATION; N-HETEROCYCLIC CARBENE; ORGANIC-REACTIONS; ALLYLIC ALCOHOLS; STABILIZED CARBANIONS; ASYMMETRIC-SYNTHESIS;

D O I：

10.1021/jo1012515

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The bicyclic triaminophosphine P(RNCH2CH2)(3)N (R = i-Bu, 1c) serves as an effective promoter for the room-temperature stereoselective synthesis of alpha,beta-unsaturated esters, fluorides, and nitriles from a wide array of aromatic, aliphatic, heterocyclic, and cyclic aldehydes and ketones, using a range of Wadsworth-Emmons (WE) phosphonates. Among the analogues of 1c [R = Me (1a), i-Pr (1b), Bn (1d)], 1a and 1b performed well, although longer reaction times were involved, and Id led to poorer yields than 1c. Functionalities such as cyano, chloro, bromo, methoxy, amino, ester, and nitro were well tolerated. We were able to isolate and characterize (by X-ray means; see above) the reactive WE intermediate species formed from 2b and 1c.

引用

页码：7166 / 7174

页数：9

共 23 条

[1] ORGN 311-P(i-BuNCH2CH2)3N: An efficient nonionic Lewis base as promoter for room-temperature synthesis of α,β-unsaturated esters, fluorides, ketones and nitriles using Wadsworth-Emmons phosphonates
Chintareddy, Venkat Reddy
Verkade, John G.
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2009, 237
[2] P(RNCH2CH2)3N: An efficient room-temperature promoter for the synthesis of a,b-unsaturated esters, fluorides and nitriles using Wadsworth-Emmons phosphonates
Reddy, Venkat Reddy Chinta
Verkade, John G.
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2007, 233
[3] P[N(i-Bu)CH2CH2]3N:: A versatile ligand for the Pd-catalyzed amination of aryl chlorides
Urgaonkar, S
Nagarajan, M
Verkade, JG
ORGANIC LETTERS, 2003, 5 (06) : 815 - 818
[4] P[n(i-Bu)CH2CH2]3N:: A versatile ligand for the Pd-catalyzed amination of aryl chlorides.
Verkade, JG
Urgaonkar, S
Nagarajan, M
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2003, 225 : U286 - U286
[5] P[N(iBu)CH2CH2]3N:: A versatile non-ionic base for the synthesis of higher coordinate' silicates
Kingston, JV
Verkade, JG
INORGANIC CHEMISTRY COMMUNICATIONS, 2005, 8 (07) : 643 - 646
[6] P(i-PrNCH2CH2)3N as a Lewis Base Catalyst for the Synthesis of β-Hydroxynitriles Using TMSAN
Wadhwa, Kuldeep
Verkade, John G.
JOURNAL OF ORGANIC CHEMISTRY, 2009, 74 (15): : 5683 - 5686
[7] ORGN 315-P(i-PrNCH2CH2)3N: An efficient synthesis of β-hydroxyesters and α,β-unsaturated esters using TMSEA
Wadhwa, Kuldeep
Verkade, John G.
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2009, 237
[8] P(RNCH2CH2)3N:: an efficient promoter for the direct synthesis of E-α,β-unsaturated esters
Kisanga, P
D'Sa, B
Verkade, J
TETRAHEDRON, 2001, 57 (38) : 8047 - 8052
[9] P(i-PrNCH2CH2)3N: Efficient Catalyst for Synthesizing β-Hydroxyesters and α,β-Unsaturated Esters using α-Trimethylsilylethylacetate (TMSEA)
Wadhwa, Kuldeep
Verkade, John G.
JOURNAL OF ORGANIC CHEMISTRY, 2009, 74 (11): : 4368 - 4371
[10] P(i-PrNCH2CH2)3N:: An efficient nonionic catalyst for the regioselective Michael addition of a β,γ-unsaturated ester and a nitrile
Wroblewski, AE
Bansal, V
Kisanga, P
Verkade, JG
TETRAHEDRON, 2003, 59 (04) : 561 - 566

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