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Silyl palladium cations (R3P)2Pd–SiR3+ catalyze the ring opening, C–C bond forming, and functionalization of 5- and 6-membered cyclic allyl ethers with O-silyl nucleophiles. Conditions for high regio-control are achieved by adjustments in the phosphine electronics, with the identity of the 2-substituent also influencing the functionalization location in unsymmetrical furans. Allyl alcohols are obtained with a regio-preference for terminal addition with unsubstituted ethers with E-products being obtained with XantPhos and Z- with (4-CF3–Ar)3 ligation. Styrenes dominate with phenyl-substituted dihydrofurans, and for 2-alkyl-substituted, secondary alcohols result from an allyl migration pathway. Mechanistic studies demonstrate the feasibility of Pd–Si+ bonds to facilitate C–O activation to yield π-allyl intermediates, and for one substrate class to also sequence π-allyl migration prior to nucleophilic addition. DFT calculations demonstrated the viability of silylium-activated ether as a competent ligand for Pd(0).
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Distal Allylic/Benzylic C−H Functionalization of Silyl Ethers Using Donor/Acceptor Rhodium(II) Carbenes
Abstract Regio‐ and stereoselective distal allylic/benzylic C−H functionalization of allyl and benzyl silyl ethers was achieved using rhodium(II) carbenes derived from N‐sulfonyltriazoles and aryldiazoacetates as carbene precursors. The bulky rhodium carbenes led to highly site‐selective functionalization of less activated allylic and benzylic C−H bonds even in the presence of electronically preferred C−H bonds located α to oxygen. The dirhodium catalyst Rh2(S‐NTTL)4is the most effective chiral catalyst for triazole‐derived carbene transformations, whereas Rh2(S‐TPPTTL)4works best for carbenes derived from aryldiazoacetates. The reactions afford a variety of δ‐functionalized allyl silyl ethers with high diastereo‐ and enantioselectivity. The utility of the present method was demonstrated by its application to the synthesis of a 3,4‐disubstitutedl‐proline scaffold.
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- Award ID(s):
- 1700982
- PAR ID:
- 10139268
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 59
- Issue:
- 19
- ISSN:
- 1433-7851
- Format(s):
- Medium: X Size: p. 7397-7402
- Size(s):
- p. 7397-7402
- Sponsoring Org:
- National Science Foundation
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