We propose a framework to train supervised learning models on synthetic data to estimate brain microstructure parameters using diffusion magnetic resonance imaging (dMRI). Although further validation is necessary, the proposed framework aims to seamlessly incorporate realistic simulations into dMRI microstructure estimation. Synthetic data were generated from over 1,000 neuron meshes converted from digital neuronal reconstructions and linked to their neuroanatomical parameters (such as soma volume and neurite length) using an optimized diffusion MRI simulator that produces intracellular dMRI signals from the solution of the Bloch–Torrey partial differential equation. By combining random subsets of simulated neuron signals with a free diffusion compartment signal, we constructed a synthetic dataset containing dMRI signals and 40 tissue microstructure parameters of 1.45 million artificial brain voxels. To implement supervised learning models we chose multilayer perceptrons (MLPs) and trained them on a subset of the synthetic dataset to estimate some microstructure parameters, namely, the volume fractions of soma, neurites, and the free diffusion compartment, as well as the area fractions of soma and neurites. The trained MLPs perform satisfactorily on the synthetic test sets and give promising in-vivo parameter maps on the MGH Connectome Diffusion Microstructure Dataset (CDMD). Most importantly, the estimated volume fractions showed low dependence on the diffusion time, the diffusion time independence of the estimated parameters being a desired property of quantitative microstructure imaging. The synthetic dataset we generated will be valuable for the validation of models that map between the dMRI signals and microstructure parameters. The surface meshes and microstructures parameters of the aforementioned neurons have been made publicly available.