undefined locant + underspecified phosphorus/sulfur atom = match

[IngvarLa]

Hi Daniel, Think this sums up several of the issues I have seen. When there is a halogen atom/amino group without a locant and there is a tetravalent phosphorous/pentavalent sulfur atom, the halogen should in most cases go to the P/S.

If I search for: Pv5+0:1(Cl).[NX3v3+0:2]>>[P:1]=[N:2] in Pistachio, I get 200+ hits, non of them intended, some examples:

(2S)-butyl 2-(chloro(phenoxy)phosphorylamino)propanoate: ClC1=C(OP(=O)=NC@HC)C=CC=C1 This one givers a warning: APPEARS_AMBIGUOUS: Connection of chloro to phenoxy Move the amino and the chlorine ends up on the P as intended: (2S)-butyl 2-(chloro(phenoxy)phosphoryl)aminopropanoate: ClP(=O)(OC1=CC=CC=C1)NC@HC

(2S)-cyclohexyl 2-(chloro(naphthalen-1-yloxy)-phosphorylamino)-3-methylbutanoate I get: ClC1=C(C2=CC=CC=C2C=C1)OP(=O)=NC@HC(C)C Moving the chloro to: (2S)-cyclohexyl 2-((naphthalen-1-yloxy)-chlorophosphorylamino)-3-methylbutanoate I get: C1(=CC=CC2=CC=CC=C12)OP(=O)(Cl)NC@HC(C)C which is what was intended.

Here the benzylamino and amino groups do not have locants: (2S)-Neopentyl 2-((((2R,3R,4R,5R)-5-(2-amino-6-methoxy-9H-purin-9-yl)-3,4-dihydroxy-4-methyltetrahydrofuran-2-yl)methoxy)(benzylamino)phosphorylamino)propanoate NC1=NC(=C2N=CN(C2=N1)[C@H]1C@(C)O)OC move one of the aminos to: (2S)-Neopentyl 2-((((2R,3R,4R,5R)-5-(2-amino-6-methoxy-9H-purin-9-yl)-3,4-dihydroxy-4-methyltetrahydrofuran-2-yl)methoxy)(benzylamino)phosphoryl)aminopropanoate I get the intended: NC1=NC(=C2N=CN(C2=N1)[C@H]1C@(C)O)OC

In all three cases ChemDraw treats the names as equivalent