Which electronic effects are responsible for the reduction of nucleophilicity of a hydroxy group orthogonal to an ester?
If we focus on the 2-oxo-3s-hydroxy-tetrahydrofuran the electronic  effects present are the hyperconjugation and the dipole minimization. "Both effects contribute to the preferred (Z)-conformation of esters over the (E)-conformation. In the (Z) conformation, the lone pair of electrons in the alpha oxygen can donate into the neighboring σ* C-O orbital. In addition, the dipole is minimized in the (Z)-conformation and maximized in the (E)-conformation. But this electronic effects occur between the carbonyl carbon and the oxygen of the ring but the hydroxyl group." [a] 



In contrast, I calculated the PES of hydroxy group in the following two systems:


2-oxo-3s-hydroxy-tetrahydrofuran [S1]
(1S,2S)-isopropyl 1-hydroxy-2-((vinyloxy)methyl)cyclohexanecarboxylate 


The latter one is:



The oxygen of iprO-(C=O)- group was pointed away from [S2] and towards to [S3] cyclohexane. The PES is: (It was calculated with am1 due to computational resources, it was done with my laptop.)



It can be observed that the intramolecular hydrogen bond (IHB) in [S3] is more stable than in the other systems. The order of intramolecular hydrogen bond preference is [S3]>[S2]>[S1]. In other words, the IHB formed with the oxygen SP$^3$ of iprO-(C=O)- group is preferred over the carbonyl oxygen. [b] This can be seen on the rotational barrier between both minima. This conformational preference allows the lone pair of hydroxyl oxygen to be more nucleophilic than in the other systems. As it can be seen in the following figures:

[S1]



[S2]



[S3]



Related to the electronic effects present in this IHB, it can be complemented that "this is a consequence of interacting the lone pair on the accepting oxygen with an empty hydride antibond of the donating O-H atoms, $n_O$ → $\sigma^*OH$. Occupancy of the antibonding orbital raises the energy of the O-H species while stabilizing the oxygen." As Albrecht et. al. concluded in her paper.[c]

Bibliography


[a] Cuevas, Eusebio Juaristi, Gabriel (1995). The anomeric effect. Boca Raton: CRC Press. ISBN 0-8493-8941-0.
[b] Rincon et al. J Solution Chem (2011) 40: 656.
[c] Albrecht et al. J. Phys. Chem. A. (2012) 116: 3946