تفاعل الألدول

(تم التحويل من Aldol reaction)

تفاعل الألدول هو aldol reaction وسيلة لتشكيل روابط الكربون-كربون في الكمياء العضوية.[1][2][3] اكتشفه بشكل مستقل تشارلز-أدولف ڤورتز[4][5][6] وألكسندر بورودين عام 1872،[7]


A typical experimental setup for an aldol reaction.
The flask on the right is a solution of lithium diisopropylamide (LDA) in tetrahydrofuran (THF). The flask on the left is a solution of the lithium enolate of tert-butyl propionate (formed by addition of LDA to tert-butyl propionate). An aldehyde can then be added to the enolate flask to initiate an aldol addition reaction.
Both flasks are submerged in a dry ice/acetone cooling bath (−78 °C) the temperature of which is being monitored by a thermocouple (the wire on the left).

الآليات

A generalized view of the Aldol reaction
A generalized view of the Aldol reaction

آلية الإنول

Mechanism for acid-catalyzed aldol reaction of an aldehyde with itself
Mechanism for acid-catalyzed aldol reaction of an aldehyde with itself
Mechanism for acid-catalyzed dehydration of an aldol
Mechanism for acid-catalyzed dehydration of an aldol


آلية الإنولات

Simple mechanism for base-catalyzed aldol reaction of an aldehyde with itself
Simple mechanism for base-catalyzed aldol reaction of an aldehyde with itself
Simple mechanism for the dehydration of an aldol product
Simple mechanism for the dehydration of an aldol product

نموذج زيمرمان-تريكسلر

The Zimmerman–Traxler model
The Zimmerman–Traxler model

السيطرة المتفاعلة عبر الأدول

Hypothetical aldol reaction
Hypothetical aldol reaction


Four possible aldol reaction products
Four possible aldol reaction products


الحموضة

Acidic control of the aldol reaction
Acidic control of the aldol reaction


ترتيب الإضافة

الإنولات

Stereoelectronic deprotonation requirements
Stereoelectronic deprotonation requirements

الهندسة

Stereoselective enolate generation
Stereoselective enolate generation
Effect of HMPA addition
Effect of HMPA addition
The Ireland model
The Ireland model


الكيمياء الموضعية

Kinetic and thermodynamic enolates
Kinetic and thermodynamic enolates


Stereoselectivity

Syn and anti products from an aldol reaction
Syn and anti products from an aldol reaction


هندسة الإنوليت

Anti-aldol formation via E-enolate
Anti-aldol formation via E-enolate
Syn-aldol formation via Z-enolate
Syn-aldol formation via Z-enolate

أيو الفلز

Aldol reaction with enolate-based stereocontrol
Aldol reaction with enolate-based stereocontrol
General model of the aldol reaction with enolate-based stereocontrol
General model of the aldol reaction with enolate-based stereocontrol


Aldol reaction with enolate-based stereocontrol
Aldol reaction with enolate-based stereocontrol


The general model of the aldol reaction with carbonyl-based stereocontrol
The general model of the aldol reaction with carbonyl-based stereocontrol
Examples of the aldol reaction with carbonyl-based stereocontrol
Examples of the aldol reaction with carbonyl-based stereocontrol


=كمياء أوكسزوليدينون إيفانز

Aldol reaction creates stereoisomers
Aldol reaction creates stereoisomers
Four possible stereoisomers of the aldol reaction
Four possible stereoisomers of the aldol reaction




Evans' chiral oxazolidinone cleavage
Evans' chiral oxazolidinone cleavage

الاختفالات والطرق الحديثة

تفاعلات خلات الأدول

تفاعل أدول موكايايما

Crimmins thiazolidinethione aldol

Organocatalysis


إضافات الأدول "المباشرة"




تفاعلات الأدول البيولوجية

انظر أيضاً

المصادر

  1. ^ Wade, L. G. (2005). Organic Chemistry (6th ed.). Upper Saddle River, New Jersey: Prentice Hall. pp. 1056–66. ISBN 0-13-236731-9.
  2. ^ Smith, M. B.; March, J. (2001). Advanced Organic Chemistry (5th ed.). New York: Wiley Interscience. pp. 1218–23. ISBN 0-471-58589-0.
  3. ^ Mahrwald, R. (2004). Modern Aldol Reactions, Volumes 1 and 2. Weinheim, Germany: Wiley-VCH Verlag GmbH & Co. KGaA. pp. 1218–23. ISBN 3-527-30714-1.
  4. ^ Wurtz, C. A. (1872). Bull. Soc. Chim. Fr. 17: 436–442.{{cite journal}}: CS1 maint: untitled periodical (link)
  5. ^ Wurtz, C. A. (1872). "Ueber einen Aldehyd-Alkohol". Journal für Praktische Chemie. 5 (1): 457–464. doi:10.1002/prac.18720050148.
  6. ^ Wurtz, C. A. (1872). "Sur un aldéhyde-alcool". Comptes rendus de l'Académie des sciences (in French). 74: 1361.{{cite journal}}: CS1 maint: unrecognized language (link)
  7. ^ Borodin observed the dimerization of acetaldehyde to 3-hydroxybutanal under acidic conditions

وصلات خارجية