Journal
ORGANOMETALLICS
Volume 35, Issue 15, Pages 2473-2479Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.organomet.6b00347
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Funding
- 973 Program [2012CB215305]
- NSFC [21325208, 21402181, 21572212]
- IPDFHCPST [2014FXCX006]
- CAS [KFJ-EW-STS-051, YZ201563]
- FRFCU
- PCSIRT
- National Supercomputing Center in Shenzhen
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Density functional theory (DFT) calculations have been performed to study the mechanism of Ir(III) pincer complex (POCOP)Ir(H)(acetone)(+) (POCOP = 2,6-bis(dibutylphosphinito)phenyl) catalyzed chemoselective C1 O hydrosilylative reduction of glucose. The mechanisms for reduction of the external and internal C1-0 (i.e., C1-O-ext and C1-O-int) on the C1-MeO-substituted glucose (i.e., 1(Me)) and C1-Me2EtSiO-substituted glucose (i.e., 1(Si)) have been investigated. The calculation results show that both mechanisms proceed with the first concerted silyl transfer and the subsequent C1-O-ext or C1-O-int bond cleavage and hydride transfer steps. In the hydride transfer step, the Ir-H moiety acts as the hydride source. The C1-O cleavage is the rate-determining step of the overall mechanism. The Cl-O-ext reduction is more favorable than C1-O-int reduction for the substrate '&, while the C1-O-int reduction is more favorable for lsi. These results are consistent with the recent experimental outcomes. Analyzing the origin of chemoselectivity for the C1-O-int or Cl Oint cleavage, we found that the more stable precursor of C1-O-ext cleavage and retention of the six-membered-ring structure result in the selective Cl-O-ext reduction of lme. Meanwhile, the higher basicity of the alkyl ether O-int atom (in comparison to the silyl ether 0' atom) and greater steric hindrance in the precursor favor the C1-O-int bond weakening. Therefore, the Cl Oint reduction occurs selectively for 1(Si).
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