TY - JOUR
T1 - Relay ring-closing metathesis (RRCM)
T2 - A strategy for directing metal movement throughout olefin metathesis sequences
AU - Hoye, Thomas R.
AU - Jeffrey, Christopher S.
AU - Tennakoon, Manomi A.
AU - Wang, Jizhou
AU - Zhao, Hongyu
PY - 2004/8/25
Y1 - 2004/8/25
N2 - The title concept involves the use of structurally modified RCM substrates that contain extender arms, terminating in a remote reactive alkene. Initiation of an RCM sequence at that reactive alkene is followed by rapid intramolecular relay of the metal center to an initially less reactive alkene in the parent substrate. This permits one to control the relative timing (or direction) of a metathesis sequence. For example, one can reverse the inherent tendency of an unsymmetrical α,ω-diene substrate to close, say, left-to-right, to that of right-to-left. Four distinct types of application of the RRCM concept are demonstrated. Among other things, they show the preparation of tetrasubstituted electron-deficient alkenes using G1 [(Cy3P)2(Cl2)Ru=CHPh], complementary control of directionality (endedness), auxiliary benefits (enzyme specificity) from the incorporation of additional steric bulk, the activation of otherwise ineffective substrates for RCM closure, the use of unorthodox alkenes as initiation sites for ring closure, and control of product olefin geometry.
AB - The title concept involves the use of structurally modified RCM substrates that contain extender arms, terminating in a remote reactive alkene. Initiation of an RCM sequence at that reactive alkene is followed by rapid intramolecular relay of the metal center to an initially less reactive alkene in the parent substrate. This permits one to control the relative timing (or direction) of a metathesis sequence. For example, one can reverse the inherent tendency of an unsymmetrical α,ω-diene substrate to close, say, left-to-right, to that of right-to-left. Four distinct types of application of the RRCM concept are demonstrated. Among other things, they show the preparation of tetrasubstituted electron-deficient alkenes using G1 [(Cy3P)2(Cl2)Ru=CHPh], complementary control of directionality (endedness), auxiliary benefits (enzyme specificity) from the incorporation of additional steric bulk, the activation of otherwise ineffective substrates for RCM closure, the use of unorthodox alkenes as initiation sites for ring closure, and control of product olefin geometry.
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U2 - 10.1021/ja046385t
DO - 10.1021/ja046385t
M3 - Article
C2 - 15315410
AN - SCOPUS:4143062538
SN - 0002-7863
VL - 126
SP - 10210
EP - 10211
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 33
ER -