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Chem 341 Organic Chemistry I

Lecture Summary 27 October 29, 2007


Chapter 9 - Stereochemistry Meso Compounds Meso Compounds are molecules that contain stereogenic carbons, but are not chiral. Their mirror images are identical. This occurs when there is a plane of symmetry in the molecule. Here are some more examples.
MESO O HO HO O MESO CH3 CH3 H3C H3C OH OH HO HO O O OH OH OH OH ENANTIOMERS CH3 CH3 H3C H3C HO OH HO O OH HO ENANTIOMERS O OH

Prochiral Compounds Molecules that are achiral but can form a new stereogenic carbon during a reaction is called prochiral. An example is shown in the addition of HBr to an alkene. Note again that without anything else chiral influencing the reaction, a racemic mixture is obtained.

HBr

Br

R + Br 50:50

S Br

Aldehydes and ketones are also prochiral. Addition of a nucleophile to the top or bottom face would produce opposition enantiomers.

O R H aldehyde

Nuc

HO Nuc + R H

Nuc R

OH H

O R R2 ketone

Nuc

HO Nuc R R2 +

Nuc R

OH R2

2007 Gregory R. Cook North Dakota State University

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Chem 341

We define the faces of an aldehyde or ketone based on the clockwise or counterclockwise order of group priorities. We call the face where you would move clockwise the Re (ree) face and the face affording a counterclockwise order of priorities the Si (sigh) face. Note that addition of a nucleophile to the Re or Si face of a carbonyl compound does not necessarily translate into the formation of an R or S product. That depends on the relative priorities of the four groups.
1 O 3 H R 2 2 R 1 O H 3 R O H Re face addition Si face addition

Re face

Si face

Re face addition O CH3 H CH2CH3 HO H (R) CH3 + CH2CH3

Si face addition H3C OH H (S) CH2CH3

O CN H CH2CH3

HO H

CN + CH2CH3

NC OH H (R) CH2CH3

(S)

Stereochemistry of Other Atoms Other atoms besides carbon have an asymmetric tetrahedral geometry. For example, when you consider the lone pair on nitrogen, and there are three different groups attached, the molecule will not be the same as its mirror image. However, Nitrogen compounds will invert very rapidly at room temperature and are thus always present as a racemic mixture. Therefore, they do not possess any properties of being chiral (eg. Rotate plane polarized light). Phosphine compounds invert much more slowly and can be isolated as chiral entities. They do not racemize unless heated.

N B C

B A

N C

B N

C A

enantiomers

2007 Gregory R. Cook North Dakota State University

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Chem 341

NO INVERSION AT ROOM TEMP


P B C A

A C

P B

enantiomers

Chapter 10 - Alkyl Halides Alkyl halides are common Organic halogen compounds are found in many places from common solvents for chemistry and industry, to refrigerants (largely banned for their ozone destruction properties) and natural products.
CH2Cl2 CHCl3 CH2Cl-CH2Cl common solvents CF2Cl2 CFCs (chlorofluorocarbons) H N N Cl natural products (epibatidine)

The chemistry of alkyl halides is dominated by the fact that the carbon-halogen bond is polarized toward the more electronegative halogen. Thus, the carbon is electrophilic. Organic fluorides are the most stable whereas the iodides are the most reactive. This correlates to the change in bond length.
diopole moment bond length (Debyes) () fluoromethane chloromethane bromomethane iodomethane CH3-F CH3-Cl CH3-Br CH3-I 1.85 1.87 1.81 1.62 1.39 1.78 1.93 2.14 bond strength (kcal/mol) 108 84 70 56

Preparation of Alkyl Halides - addition reactions Recall that alkyl halides can be prepared by addition reactions of alkenes.

H 3C C H 3C C

H + HBr H

H 3C H3C

H C C H H

Br

H3C H 3C

Br H C C H H

Most stable intermediate Lower energy pathway


Br Br-Br A bromonium Br Br

Br

Bromide can only come from the bottom and kick off the bromine on the top. This reaction forms the trans product selectively.

2007 Gregory R. Cook North Dakota State University

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Chem 341

Quiz of the day

2007 Gregory R. Cook North Dakota State University

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Chem 341