Mechanistic Understanding of Proline Analogs and Related Protic Lewis Bases (n - π*)

Alan Armstrong*, Paul Dingwall

*Corresponding author for this work

Research output: Chapter in Book/Report/Conference proceedingChapter

Abstract

Proline has played a pivotal role in the development of the field of organocatalysis and is regarded by many as the archetypal organocatalyst. Indeed, proline has been known as a catalyst of the intramolecular aldol reaction since the 1970s, in what was originally thought to be a solitary example of novel reactivity. A mechanistic understanding of proline catalysis has the potential to allow the design of improved catalysts and reaction conditions. The chapter discusses the mechanism of the proline-catalyzed aldol reaction, including the Hajos-Parrish-Eder-Sauer-Wiechert (HPESW) reaction, the Houk-List model, the Seebach-Eschenmoser Model. It also discusses the proline-catalyzed α-amination and α-aminoxylation reactions. Proline-mediated conjugate addition reactions, in which the nucleophile is the carbonyl α-carbon, were first reported in 2001. Then, the chapter explains the modified proline derivatives including proline tetrazole, and the Houk-List model and proline analogs.

Original languageEnglish
Title of host publicationLewis Base Catalysis in Organic Synthesis
PublisherWiley-VCH Verlag
Pages145-190
Number of pages46
Volume1
ISBN (Electronic)9783527675142
ISBN (Print)9783527336180
DOIs
Publication statusPublished - 17 Aug 2016

Fingerprint

Lewis Bases
Proline
Amination
Nucleophiles
Addition reactions
Catalysts
Catalysis
Carbon
Derivatives

Keywords

  • Additives
  • Aldol
  • DFT
  • Enamine
  • Hajos-Parrish-Eder-Sauer-Wiechert (HPESW) reaction
  • Houk-List model
  • Iminium ion
  • Mechanism
  • Prolinate catalyst
  • Proline catalyst
  • Proline derivative catalysts
  • Reaction kinetics
  • Seebach-Eschenmoser model
  • α-amination
  • α-aminoxylation

Cite this

Armstrong, A., & Dingwall, P. (2016). Mechanistic Understanding of Proline Analogs and Related Protic Lewis Bases (n - π*). In Lewis Base Catalysis in Organic Synthesis (Vol. 1, pp. 145-190). Wiley-VCH Verlag. https://doi.org/10.1002/9783527675142.ch6
Armstrong, Alan ; Dingwall, Paul. / Mechanistic Understanding of Proline Analogs and Related Protic Lewis Bases (n - π*). Lewis Base Catalysis in Organic Synthesis. Vol. 1 Wiley-VCH Verlag, 2016. pp. 145-190
@inbook{f204a8e19ad743b0806617d5eebb8737,
title = "Mechanistic Understanding of Proline Analogs and Related Protic Lewis Bases (n - π*)",
abstract = "Proline has played a pivotal role in the development of the field of organocatalysis and is regarded by many as the archetypal organocatalyst. Indeed, proline has been known as a catalyst of the intramolecular aldol reaction since the 1970s, in what was originally thought to be a solitary example of novel reactivity. A mechanistic understanding of proline catalysis has the potential to allow the design of improved catalysts and reaction conditions. The chapter discusses the mechanism of the proline-catalyzed aldol reaction, including the Hajos-Parrish-Eder-Sauer-Wiechert (HPESW) reaction, the Houk-List model, the Seebach-Eschenmoser Model. It also discusses the proline-catalyzed α-amination and α-aminoxylation reactions. Proline-mediated conjugate addition reactions, in which the nucleophile is the carbonyl α-carbon, were first reported in 2001. Then, the chapter explains the modified proline derivatives including proline tetrazole, and the Houk-List model and proline analogs.",
keywords = "Additives, Aldol, DFT, Enamine, Hajos-Parrish-Eder-Sauer-Wiechert (HPESW) reaction, Houk-List model, Iminium ion, Mechanism, Prolinate catalyst, Proline catalyst, Proline derivative catalysts, Reaction kinetics, Seebach-Eschenmoser model, α-amination, α-aminoxylation",
author = "Alan Armstrong and Paul Dingwall",
year = "2016",
month = "8",
day = "17",
doi = "10.1002/9783527675142.ch6",
language = "English",
isbn = "9783527336180",
volume = "1",
pages = "145--190",
booktitle = "Lewis Base Catalysis in Organic Synthesis",
publisher = "Wiley-VCH Verlag",
address = "Germany",

}

Armstrong, A & Dingwall, P 2016, Mechanistic Understanding of Proline Analogs and Related Protic Lewis Bases (n - π*). in Lewis Base Catalysis in Organic Synthesis. vol. 1, Wiley-VCH Verlag, pp. 145-190. https://doi.org/10.1002/9783527675142.ch6

Mechanistic Understanding of Proline Analogs and Related Protic Lewis Bases (n - π*). / Armstrong, Alan; Dingwall, Paul.

Lewis Base Catalysis in Organic Synthesis. Vol. 1 Wiley-VCH Verlag, 2016. p. 145-190.

Research output: Chapter in Book/Report/Conference proceedingChapter

TY - CHAP

T1 - Mechanistic Understanding of Proline Analogs and Related Protic Lewis Bases (n - π*)

AU - Armstrong, Alan

AU - Dingwall, Paul

PY - 2016/8/17

Y1 - 2016/8/17

N2 - Proline has played a pivotal role in the development of the field of organocatalysis and is regarded by many as the archetypal organocatalyst. Indeed, proline has been known as a catalyst of the intramolecular aldol reaction since the 1970s, in what was originally thought to be a solitary example of novel reactivity. A mechanistic understanding of proline catalysis has the potential to allow the design of improved catalysts and reaction conditions. The chapter discusses the mechanism of the proline-catalyzed aldol reaction, including the Hajos-Parrish-Eder-Sauer-Wiechert (HPESW) reaction, the Houk-List model, the Seebach-Eschenmoser Model. It also discusses the proline-catalyzed α-amination and α-aminoxylation reactions. Proline-mediated conjugate addition reactions, in which the nucleophile is the carbonyl α-carbon, were first reported in 2001. Then, the chapter explains the modified proline derivatives including proline tetrazole, and the Houk-List model and proline analogs.

AB - Proline has played a pivotal role in the development of the field of organocatalysis and is regarded by many as the archetypal organocatalyst. Indeed, proline has been known as a catalyst of the intramolecular aldol reaction since the 1970s, in what was originally thought to be a solitary example of novel reactivity. A mechanistic understanding of proline catalysis has the potential to allow the design of improved catalysts and reaction conditions. The chapter discusses the mechanism of the proline-catalyzed aldol reaction, including the Hajos-Parrish-Eder-Sauer-Wiechert (HPESW) reaction, the Houk-List model, the Seebach-Eschenmoser Model. It also discusses the proline-catalyzed α-amination and α-aminoxylation reactions. Proline-mediated conjugate addition reactions, in which the nucleophile is the carbonyl α-carbon, were first reported in 2001. Then, the chapter explains the modified proline derivatives including proline tetrazole, and the Houk-List model and proline analogs.

KW - Additives

KW - Aldol

KW - DFT

KW - Enamine

KW - Hajos-Parrish-Eder-Sauer-Wiechert (HPESW) reaction

KW - Houk-List model

KW - Iminium ion

KW - Mechanism

KW - Prolinate catalyst

KW - Proline catalyst

KW - Proline derivative catalysts

KW - Reaction kinetics

KW - Seebach-Eschenmoser model

KW - α-amination

KW - α-aminoxylation

UR - http://www.scopus.com/inward/record.url?scp=85018255588&partnerID=8YFLogxK

U2 - 10.1002/9783527675142.ch6

DO - 10.1002/9783527675142.ch6

M3 - Chapter

AN - SCOPUS:85018255588

SN - 9783527336180

VL - 1

SP - 145

EP - 190

BT - Lewis Base Catalysis in Organic Synthesis

PB - Wiley-VCH Verlag

ER -

Armstrong A, Dingwall P. Mechanistic Understanding of Proline Analogs and Related Protic Lewis Bases (n - π*). In Lewis Base Catalysis in Organic Synthesis. Vol. 1. Wiley-VCH Verlag. 2016. p. 145-190 https://doi.org/10.1002/9783527675142.ch6