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

[21] P(PhCH2NCH2CH2)3N: An Efficient Lewis Base Catalyst for the Synthesis of Propargylic Alcohols and Morita-Baylis-Hillman Adducts via Aldehyde Alkynylation
Wadhwa, Kuldeep
Chintareddy, Venkat Reddy
Verkade, John G.
JOURNAL OF ORGANIC CHEMISTRY, 2009, 74 (17): : 6681 - 6690
[22] Alkyl phosphazines, (C6H5)(3)PNNC(R-1)(R-2): [i) R-1=CH3; R-2=i-Bu and ii) R-1=R-2=C6H5CH2-]. Synthesis, conversion to methyl iodide salt and single crystal X-ray structure of phosphazinium bromide, [(C6H5)(3)P=N(H)N=C(CH3)(i-Bu)]Br-+(-)
Senthivel, P
Rao, MNS
Srinivas, J
Murthy, GS
PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS, 1996, 117 : 179 - 187
[23] ACTIVATION OF AN ALIPHATIC C-H BOND AT ROOM-TEMPERATURE - CONVERSION ON A CLUSTER OF A STABLE SIGMA-BONDED ALKYL GROUP TO A MU-2-ALKYLIDENE LIGAND - SYNTHESIS AND CRYSTAL-STRUCTURE DETERMINATION OF HOS3(6-CH2C5H3N-2-C(H)=N-I-PR)(CO)9 AND H2OS3(6-CHC5H3N-2-C(H)=N-I-PR)(CO)8
ZOET, R
VANKOTEN, G
VRIEZE, K
JANSEN, J
GOUBITZ, K
STAM, CH
ORGANOMETALLICS, 1988, 7 (07) : 1565 - 1572

← 1 2 3 →