Dear Andrew,

that functional group is a sulfoxide, and it is indeed chiral because 
has a lone pair on the sulfur, which is pyramidal; there is a short 
description here:
https://en.wikipedia.org/wiki/Sulfoxide

So it is the same (R,S) chirality you would have on a tetrahedral 
carbon. The carbon analogue of a sulfoxide, that is a carbonyl group, is 
planar and therefore is not chiral; this explains why you lose the 
chirality.

Kind regards,
Paolo

On 08/02/2016 15:05, Andrew Dalke wrote:
> Hi!
>
>    Could someone explain to this non-chemist what the chirality means in the 
> following?
>
>    CN[S@@](=O)C1=CC=CC=C1
>
> It comes from PubChem id 12194260 at 
> https://pubchem.ncbi.nlm.nih.gov/compound/12194260 .
>
> Isn't this a symmetric structure, which can't have an orientation at that 
> point? Even if it can have a chirality, which sort of chirality is it? The 
> list at http://www.daylight.com/dayhtml/doc/theory/theory.smiles.html says:
>
>    Tetrahedral is the default class for degree four
>    Allene-like is the default class for degree 2
>    Square-planar is another class for degree four
>    Trigonal-bipyramidal is the default class for degree five
>    Octahedral is the default class for degree six
>
> but says nothing about degree three. And RDKit agrees that this is degree 3:
>
>    >>> mol = Chem.MolFromSmiles("CN[S@@](=O)C1=CC=CC=C1")
>    >>> mol.GetAtomWithIdx(2).GetDegree()
>    3
>
>
> This came up while testing my algorithm to fragment a structure. I expect to 
> get the same structure back.
>
> I started with:
>
>    >>> Chem.CanonSmiles("CN[S@@](=O)C1=CC=CC=C1")
>    'CN[S@@](=O)c1ccccc1'
>
> The fragmentation produces:
>
>    >>> Chem.CanonSmiles("C*.N*.*[S@@](=O)C1=CC=CC=C1")
>    '[*]C.[*]N.[*][S@@](=O)c1ccccc1'
>
> I can manipulate this at the SMILES level to insert two closures and produce 
> the reconnect-able SMILES
>
>      C2.N23.[S@@]3(=O)C1=CC=CC=C1
>       ^--^
>           ^------^
>
> When I process that, I get a flipped chirality:
>
>    >>> Chem.CanonSmiles("C2.N23.[S@@]3(=O)C1=CC=CC=C1")
>    'CN[S@](=O)c1ccccc1'
>
> I did not expect this. The Daylight SMILES spec says:
>
>    The chiral order of the ring closure bond is implied by the
>    lexical order that the ring closure digit appears on the
>    chiral atom (not in the lexical order of the "substituent" atom).
>
> I expected the '*' of '*[S**]' and the '3' of '[S**]3' to have the same bond 
> position so give the same chirality.
>
> Finally, if I replace the '[S@@]' with a '[C@@]' or '[P@@]' I lose the 
> chirality:
>
>    >>> Chem.CanonSmiles("CN[C@@](=O)C1=CC=CC=C1")
>    'CNC(=O)c1ccccc1'
>    >>> Chem.CanonSmiles("CN[P@@](=O)C1=CC=CC=C1")
>    'CN[P](=O)c1ccccc1'
>
>
> At this point I can't tell if there's a problem with how I understand 
> stereochemistry, how I understand SMILES, or how I understand RDKit.
>
>
>
>                               Andrew
>                               da...@dalkescientific.com
>
>
>
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