In more detail, α-deprotona=on of 2 via reac=on with lithium diisopropylamide (LDA) followed by 𝛼-hydroxyla=on with (1R)-(-)-(camphorsulfonyl)oxaziridine afforded the 𝛼-hydroxy-ester 3 (61%). Evalua=ng a range of condi=ons demonstrated that addi=on of TMEDA was cri=cal for the desired product forma=on. Notably, our ini=al efforts at saponifica=on of 3 and subsequent iodolactoniza=on resulted in the cycliza=on of the direc=ng OH func=onality to a bicyclic ether, rather than the desired intramolecular nucleophilic aback of the carboxyl group (Supplementary Fig. ). To circumvent the undesired cycliza=on, the OH func=onality was acetylated by reac=on with ace=c anhydride, enabling efficient iodolactoniza=on of the intermediate acid to give 4 in 73% yield over 3 steps. Following DBU-mediated elimina=on to 5 (56%), simultaneous basecatalyzed ring-opening and deprotec=on resulted in the desired single diastereomer 6 (59%). Photoisomeriza=on of 7 and con=nuous ac=ve removal of trans-cyclooctene isomers by using Ag(I)immobilized on sulfonated silica gel 46 yielded the desired bis-axial diastereomer ax-7 (35%) as the most abundant product, along with its bis-equatorial counterpart equ-7 (25%). Given the func=onal configura=on of the axial diastereomer ax-7, we used this iTCO building block for further modifica=on. Ac=va=on of the allylic OH group was achieved by reac=on with p-nitrophenyl (PNP) chloroformate, yielding iTCO-PNP carbonate (81%) as a reagent for the prepara=on of click-cleavable iTCO-carbamates (see Supplementary Informa=on).