ऋषिसत्तमः गुरुसत्तमः I.e. सत्तम is the second member of the compound.
but
सद्गुरुः I.e. सत् is the first member of the compound.
Thanks,
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उत्तमगुरुः , गुरूत्तमः both are frequent.
But सत्तमगुरुः is not found used while गुरुसत्तमः is abundantly used. So गुरुसत्तमः is felt normal and as such accepted.
03051011a एतस्मिन्न् एव काले तु पुराणाव् ऋषिसत्तमौ
03051011c अटमानौ महात्मानाव् इन्द्रलोकम् इतो गतौ
but in searching the whole of GRETIL I could only find one case of a compound with सत्तम as the first member. That was सत्तमसत्त्वम् in Jayaratha's commentary on Alaṁkāra-sarvasva by Ruyyaka.

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