Ring expansion reactions in the synthesis of macrocycles and medium-sized rings

TY - JOUR

T1 - Ring expansion reactions in the synthesis of macrocycles and medium-sized rings

AU - Donald, James Robert

AU - Unsworth, William Paul

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PY - 2017/3/15

Y1 - 2017/3/15

N2 - Functionalised macrocycles and medium-sized rings have applications in a number of scientific fields, ranging from medicinal chemistry and supramolecular chemistry, to catalysis and nanotechnology. However, their value in these areas can be undermined by a simple, but important limitation: large ring systems are very often difficult to make. Traditional end-to-end cyclisation reactions of long linear precursors are typically unpredictable and impractical processes, mainly due to unfavourable enthalpic and entropic factors. Most published methods to make large rings focus on minimising the damage inflicted by performing the difficult cyclisation step; in contrast, ring expansion reactions enable it to be avoided altogether. In this review, we seek to highlight how 'growing' rings from existing cyclic systems via ring expansion can expedite the efficient, practical and scalable synthesis of macrocycles and medium-sized rings.

AB - Functionalised macrocycles and medium-sized rings have applications in a number of scientific fields, ranging from medicinal chemistry and supramolecular chemistry, to catalysis and nanotechnology. However, their value in these areas can be undermined by a simple, but important limitation: large ring systems are very often difficult to make. Traditional end-to-end cyclisation reactions of long linear precursors are typically unpredictable and impractical processes, mainly due to unfavourable enthalpic and entropic factors. Most published methods to make large rings focus on minimising the damage inflicted by performing the difficult cyclisation step; in contrast, ring expansion reactions enable it to be avoided altogether. In this review, we seek to highlight how 'growing' rings from existing cyclic systems via ring expansion can expedite the efficient, practical and scalable synthesis of macrocycles and medium-sized rings.

KW - Journal Article

U2 - 10.1002/chem.201700467

DO - 10.1002/chem.201700467

M3 - Review article

C2 - 28295709

SN - 0947-6539

VL - 23

SP - 8780

EP - 8799

JO - Chemistry : A European Journal

JF - Chemistry : A European Journal

ER -