Hi,

I've spent a while beating my head against this without much success,
so I figured I'd ask around.

The attached mol file contains a chiral phosphorus center; I'm trying
to figure out whether the label for that center should be R or S.
My usual approach to this is to draw the thing in Marvin Sketch and/or
Chemdraw and see what they say. Both agree that the P is (R).
The problem I have with that is that I can't really figure out why.
I'm sure the answer is simple, but I haven't been able to find it.

I've been singularly unsuccessful at coming up with the right search
phrase to google for a result.
The one explanation I was able to find for labeling these things:
http://www.chemistry.ucsc.edu/courses/palleros/PhosphatesII.pdf
makes sense to me (the O with the double bond is the highest priority
atom), but that would lead to a label of (S) for the P in the attached
molecule.

I attempted to figure this out by going back to the original CIP
papers, but that way leads to madness (and I didn't find anything in
my skim of the papers anyway).

Here's how I would go about doing the assignment... using the mol-file
numbering of the atoms:

P6 has neighbors: O4, O5, O7
Expand those out in shells...
Shell 1:
  O4 : C2
  O5 : C3
  O7 : C9
  O8 : (P)  <- because of the double bond
Shell 2:
  O4 : C2 : C1
  O5 : C3 : C1, C10
  O7 : C9 :
  O8 : (P)
Now we have a ranking in order of increasing priority: O7, O4, O5, O8.
This leads to an assignment of (S) to the P.

The only way I can find to make the Marvin/ChemDraw assignment work is
to ignore the double bond to O8 when doing the expansion and to treat
it as a naked O:
Shell 1:
  O4 : C2
  O5 : C3
  O7 : C9
  O8 :
Shell 2:
  O4 : C2 : C1
  O5 : C3 : C1, C10
  O7 : C9 :
  O8 :
This gives the ranking O8, O7, O4, O5, which is consistent with an
assignment of (R) to the P. I just can't figure out why one would do
things this way.

Anyone have any help or a clarification for this?

-greg

Attachment: chiral_phosphorous.1.mol
Description: Binary data

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