Besides this various models have been summarized, such as crams chelating model or cyclic model, cornforth model, cram reetz rules, and evans model. Crams rule free download as powerpoint presentation. R and s configuration using cahn ingold prelog priority rules leah. Not only will there be steric interactions between the s or m groups and the rgroup, but also interactions with the incoming nucleophile due to the attack trajectory. You can download free crams rule and prelog rule stereochemistry chemistry notes edurev pdf from edurev by using search above. In the reactive conformation, the carbonyl group would orient itself in such a way that it will rest between the small group and the medium group. Draw all stereoisomers for the following molecules. Crams rule major reference works wiley online library. Introduction to stereo chemistry stereochemistry chemistry notes edurev notes for chemistry is made by best teachers who have written some of the best books of chemistry. Finding the absolute configuration r and s comes as a result of ranking and order substituents, specifically by noting the configuration of the top 3 groups.
Stereochemistry subtle differences in spatial arrangements. Crams rule in stereochemistryasymmetric synthesiscrams. Crams acyclic model is a convenient mnemonic that predicts felkin products in. Learn vocabulary, terms, and more with flashcards, games, and other study tools. Cram and elhafez examined nucleophilic addition to the carbon atom of a carbonyl group adjacent to 1,2 relationship a chiral center that consisted of a carbon atom bearing three different substituents, ranked small, medium, and large according to their relative bulk. Inductive and resonance effects of substituents on. Cram in 1952 3 is an early concept relating to the prediction of stereochemistry in certain acyclic systems. The evolution of models for carbonyl addition evans group afternoon seminar sarah siska february 9, 2001. Many workers have turned to a simple dashed line instead. If a molecule has a non superimposable mirror image, it is chiral. Stereoelectronic effects, neighbouring group participation ngp, baldwins rules, crams rule and cycloaddition reactions are then discussed. As stated by donald cram of ucla in 1952, in certain noncatalytic reactions that diastereomer will predominate, which could be formed by the approach of the entering group from the least hindered side when the rotational conformation of the cc bond is such that the double bond is flanked by the two least bulky groups attached to the adjacent asymmetric center. What is the difference between crams model and felkin ahn.
If theres a tie, keep going out in both directions, one by one, until. Chemistry cram s rule and prelog rule stereochemistry chemistry notes edurev summary and exercise are very important for perfect preparation. This covers conformational aspects of acyclic and cyclic compounds. For the love of physics walter lewin may 16, 2011 duration.
Stereochemical relationship between two or more stereogenic centers. Conformational isomers those that rapidly interconvert at room temperature. Stereochemistry projecting away from the viewer projecting toward the viewer hydrogens projecting toward the viewer the convention used in this book it moves further away. Stereochemistry an introduction pdf 40p download book. Menthol is a member of the terpene family of natural products. Although the dl nomenclature appears satisfactory for carbohydrates and aamino acids it suffers. Cram in 1952, is an early concept relating to the prediction of stereochemistry in certain acyclic systems. Selectivity science 1983 219, 245 chemoselectivity. Crams rule, stereo selectivity, reduction of ketones, stereochemistry, r and s configuration. The stereochemistry of the lithium aluminium hydride reduction of.
Crams rule illustrated glossary of organic chemistry. An extension of crams idea of reactive conformation to chiral esters of. Crams rule in stereochemistryasymmetric synthesiscrams rule pdf. Love professor crams early research was in physical organic chemistry, where his notable contributions included the structure and intermediacy of phenonium ions in solvolysis reactions, the stereochemistry of carbanions in 1965 he wrote a monograph fundamentals of carbanion chemistry, and the stereochemistry of carbonyl addition reactions crams rule. The cram chelate model l o r sm nucleophile l nu sm roh l nu sm hor 1 2 3 cram or felkinanh anticram or cram chelate s small m medium l large r o met l m s nul m s r nu oh antifelkinproduct.
O ph me pch3c6h4mgbr ptolyloh ho nh 3clnh cl nh me nh h. Explain the following trends observed by midland and coworkers m. The chiral center need not be optically pure, as the relative stereochemistry will be the same for both enantiomers. An extension of crams idea of reactive conformation to chiral esters of \\alpha\ketoesterspyruvates is the prelogs rule reported in 1953 3. Stereochemistry of tetrahedral carbons, stereoisomers stereoisomers, stereocenter, chiral, enantiomers, racemic mixture, configuration of stereocenters, molecules with multiple stereocenters, tartaric acid and enantiomers. Crams rule c x diastereomeric x c, o, n faces stereogenic how does this center control the direction of attack at the trigonal carbon. Crams rule had premises and made predictions similar to prelogs. Nucleophilic additions to carbonyls stereoselectivity of. Similarly, the nucleophilic addition that follows the crams rule is referred to as crams rule type nucleophilic addition, and the corresponding major product is called the cram product. In 1952 we published the rule of steric control of asymmetric induction in. The rule of steric control of asymmetric induction in the synthesis of acyclic systems. The rule of steric control of asymmetric induction in the syntheses of acyclic systems. Draw the two molecules in their most stable chair conformers.
If a, c of highest priority, then zif a, d of highest priority, then en b a. Crams chelation modelcrams chelate rule crams chelation anticrams rule in stereochemistry duration. Not only will there be steric interactions between the s or m groups. Introduction to stereochemistry structural constitutional isomers compounds of the same molecular formula with different connectivity structure, constitution conformational isomers compounds of the same structure that differ in rotation around one or more single bonds configurational isomers or stereoisomers compounds of the same structure that differ in one or more. The crams rule of asymmetric induction developed by donald j. As stated by donald cram of ucla in 1952, in certain noncatalytic reactions that diastereomer will predominate, which could be formed by the. Selectivity 4 felkinahn model l o m s r nu l s o m r. A potentially useful extension of crams rule is the asymmetric induction provided by a remote ester prelogs rule. Stereoselective reduction of benzoin by the nadh model 3. Crams rule predicts the major diastereomer resulting from the diastereoselective nucleophilic addition to a carbonyl group next to a chiral center. Minor product o m s r l r m s l o l m s r o l s m r o this is the important interaction that must be minimized. The molecule is generally knows as diastereotopic aldehyde or ketone in which four group are attach to the stereo. Article views are the countercompliant sum of full text article downloads since november 2008 both pdf and html across all institutions and individuals. Crams rule in stereochemistryasymmetric synthesiscrams rule pdf organic chemistry in hindi.
Why would you think this might not provide as important directing influences. It generally relates to grignard addition to chiral pyruvates made using chiral alcohols fig 1. Asymmetric induction i summary 10 concordia university. Crams rule the existing asymmetric center would have a small, medium and large group, denoted s,m and l respectively. Nucleophilic attack on acyclic carbonyl compound for certain addition to carbon oxygen double bond of aldehyde and ketone having a chiral carbon, crams rule is useful to product which diastereomers of two will predominate. Crams rule stereochemistry chemical reactions scribd. Stereochemistry as a tool in deciphering the processes of a. Stereochemistry an introduction pdf 40p this note covers the following topics. Crams rule the crams rule of asymmetric induction developed by donald j. Cram s rule c x diastereomeric x c, o, n faces stereogenic how does this center control the direction of attack at the trigonal carbon. Guidebook to mechanism in organic chemistry 6th edition. Crams rule in stereochemistryasymmetric synthesiscrams rule pdf organic chemistry in hindi duration. Prioritize the four appendages coming off the stereocenter atom using the cahningoldprelog system. Stereochemistry stereoisomers 3 fall 2011 problem 2.
You can see some cram s rule and prelog rule stereochemistry chemistry notes edurev sample questions with examples at the bottom of this page. Video 2 chiral carbons are identified as having 4 unique substituents. Selected cd and nmr methods find, read and cite all the research you. The carbonyl compound is presumed to react in a 4 these notes are alex moss 2003. Crams rule and prelog rule stereochemistry chemistry.
Chapter 34 diastereoselectivity the felkinahn model for carbonyl conformations and diastereoselective nucleophilic attack the effect of electronegative atoms on carbonyl conformation carbonyl chelation and stereoselectivity the aldol reactions chairlike transition state and stereoselective formation of syn and anti isomers. If a, c of highest priority, then syn if b, c of highest. Crams rule and felkin anh model, iit jam, tifr, csir net, set, gate, drdo. Cram or felkinanh anticram or cram chelate s small m medium l large the felkin anh model chem. Request pdf on dec 1, 2009, lorenzo di bari and others published cheminform abstract. Crams rule and prelog rule stereochemistry chemistry notes. Crams rule and modifications a purely empirical rule. L s mo r large group oriented anti to the carbonyl group cram thought that in the absence of a chelating group sterics played the biggest role in limiting the conformation of the. R and s configuration using cahn ingold prelog priority rules. Crams and felkinanh model are the models for prediction of both stereochemistry and major or minor diastereomers for 1,2asymmetric introduction, generally in the system like rcor. Crams rule and felkin anh model, iit jam, tifr, csir net, set. R o l s m o r s m l o s r m l nu nu l s nu oh m r cram felkinahn. In stereochemistry, asymmetric induction also enantioinduction describes the preferential.
In certain noncatalytic reactions that diastereomer will predominate, which could be formed by the approach of the entering group from the least hindered side when the rotational conformation of the c. To be able to predict, identify and distinguish between enantiomers and diastereoisomers. Besides this various models have been summarized, such as crams chelating model or cyclic model, cornforth model, cramreetz rules, and evans model. Request pdf on jun 1, 20, anne mengel and others published around and beyond crams rule find, read and cite all the research you need on researchgate. This rule along with its further extensions has been used to predict the stereochemistry of the nucleophilic addition product from the addition of a nucleophile to a carbonyl compound. Illustrated glossary of organic chemistry crams rule. Cram s rule and modifications a purely empirical rule. Yet, this is the most common convention used, and it is the convention we adopt in this book. They may be reproduced without need for permission. Assuming that there isnt an unusually electronegative atom on the carbon next to the carbonyl, the largest group and use the a value table for.