A cascade reaction involving sequential conjugate reduction, stereoselective aldol cyclisation and chemoselective lactone reduction mediated by SmI2–H2O provides access to a cyclopentanol bearing two vicinal quaternary stereocentres with good stereocontrol. The functionalised cyclopentanol product has been converted to a key intermediate in ongoing asymmetric studies towards stolonidiol.(4S)-1-Benzyloxy-4-(acetoxymethyl)-hept-6-en-3-oneC17H22O4Ee = 100%[α]D = +3.53 (c 0.34, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (4S)(E)-3-((3S)-6-Benzyloxy-4-oxo-3-(acetoxymethyl)-hexylidene)-tetrahydro-pyran-2-oneC21H26O6Ee = 100%[α]D = +25.14 (c 0.35, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (3S)(1R,2S,5R)-2-Acetoxymethyl-1-(2-(benzyloxy)ethyl)-1-hydroxy-6-oxo-7-oxaspiro[4.5]decaneC21H28O6Ee = 100%[α]D = −28.3 (c 0.58, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2S,5R)(1R,2S,5R)-2-Acetoxymethyl-1-hydroxy-1-(2-hydroxyethyl)-6-oxo-7-oxaspiro[4.5]decananeC14H22O6Ee = 100%[α]D = −5.12 (c 0.86, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2S,5R)(1S,2R,3S)-1-Acetoxymethyl-2-(2-(benzyloxy)ethyl)-2-hydroxy-3-(hydroxymethyl)-3-(3-hydroxypropyl)cyclopentaneC21H32O6Ee = 100%[α]D = −12.5 (c 2.50, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2R,3S)(1S,2R,3S)-1-Acetoxymethyl-2-(2-(benzyloxy)ethyl)-3-(3-((tert-butyldimethylsilyl)oxy)propyl)-2-hydroxy-3-(hydroxymethyl)cyclopentaneC27H46O6SiEe = 100%[α]D = −10.1 (c 1.45, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2R,3S)(1S,2R,3S)-1-Acetoxymethyl-2-(2-(benzyloxy)ethyl)-3-(3-((tert-butyldimethylsilyl)oxy)propyl)-2-hydroxy-3-methylcyclopentaneC27H46O5SiEe = 100%[α]D = −8.0 (c 0.55, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2R,3S)(1R,2R,3S)-Methyl-2-(2-(benzyloxy)ethyl)-3-(3-((tert-butyldimethylsilyl)oxy)propyl)-2-hydroxy-3-methylcyclopentanecarboxylateC26H44O5SiEe = 100%[α]D = −15.1 (c 1.15, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2R,3S)(1R,2S,5S)-1-(2-(Benzyloxy)ethyl)-2-(3-((tert-butyldimethylsilyl)oxy)propyl)-5-(2-hydroxypropan-2-yl)-2-methylcyclopentanolC27H48O4SiEe = 100%[α]D = −4.4 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2S,5S)(1R,2S,5S)-2-(3-((tert-Butyldimethylsilyl)oxy)propyl)-5-(2-hydroxypropan-2-yl)-2-methyl-1-vinylcyclopentanolC20H4oO3SiEe = 100%[α]D = −21.8 (c 0.9, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2S,5S)(1S,2R,3S)-1-Acetoxymethyl-3-(3-((tert-butyldimethylsilyl)oxy)propyl)-2-hydroxy-3-methyl-2-vinylcyclopentaneC20H38O4SiEe = 100%[α]D = −58.7 (c 1.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2R,3S)(1R,2S,5S)-2-(3-((tert-Butyldimethylsilyl)oxy)propyl)-5-(hydroxymethyl)-2-methyl-1-vinylcyclopentanolC18H36O3SiEe = 100%[α]D = −61.7 (c 0.92, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2S,5S)(4aS,7S,7aR)-7-(3-((tert-Butyldimethylsilyl)oxy)propyl)-7-methyl-7a-vinylhexahydrocyclopenta[d][1,3]dioxin-2-oneC19H34O4SiEe = 100%[α]D = −32.8 (c 0.72, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (4aS,7S,7aR)((5R,6S,9S)-4-(2-((Benzyloxy)methyl)allyl)-9-(((tert-butyldimethylsilyl)oxy)methyl)-6-(3-((tert-butyldimethylsilyl)oxy)propyl)-6-methyl-1,3-dioxaspiro[4.4]nonan-2-oneC35H60O6Si2Ee = 100%[α]D = −29.4 (c 0.34, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (5R,6S,9S)