Mechanistic Insight into the Reduction of Tertiary Phosphine Oxides by Ti(O<i>i</i>Pr)<sub>4</sub>/TMDS

Petit, Christelle; Favre‐Réguillon, Alain; Albela, Belén; Bonneviot, Laurent; Mignani, Gérard; Lemaire, Marc

doi:10.1021/om900747b

Cited by 88 publications

(74 citation statements)

References 43 publications

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“…The mechanism of the reaction was found to proceed via silicon radicals and Ti III species, suggesting a single electron transfer (SET) mechanism. 71 They followed these efforts up with an attractive approach to this important reduction with an InBr 3 -catalyzed TMDS reduction system (Eqs. 53 and 54).…”

Section: Tmds Reduction Of Phosphine Oxidesmentioning

confidence: 99%

Tetramethyldisiloxane: A Practical Organosilane Reducing Agent

Pesti

Larson

2016

Org. Process Res. Dev.

107

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The chemistry of tetramethyldisiloxane (TMDS) is largely composed of the reduction of functional groups with increasing applications for carboncarbon bond formation. This reagent can be a safe alternative to H 2 , LiAlH 4 , and other reactive reagents. Notable are the amide conversion to amines and aldehydes, nitro group reductions, nitrile reductions, hydrogenolysis of arylchlorine bonds, reductive formation of sulfides, reductive etherification, reductive opening of ketals, reductive demethoxylation, and formation of nitriles with homologation. Selectivity can be carried out by the choice of catalysts. This review of recent chemistry will focus on synthetically applied reactions of the recent past. Displayed reactions are chosen to be representative of the referenced work, but are also chosen to illustrate a new viewpoint. Finally, where applicable, the results of competing hydrosilanes are presented to compare to the results obtained with TMDS.

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Section: Tmds Reduction Of Phosphine Oxidesmentioning

confidence: 99%

Tetramethyldisiloxane: A Practical Organosilane Reducing Agent

Pesti

Larson

2016

Org. Process Res. Dev.

107

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“…Despite the good selectivities exhibited by these ruthenium-based catalytic systems, high CO 2 pressure is needed. [17] Herein, we report the first example of a solvent-free gramscale synthesis and isolation of a silyl formate by iridiumcatalyzed reduction of CO 2 with HMTS. The authors monitored the reaction of CO 2 with Me 3 SiH at 40 8C in the presence of [Ir(CN)(CO)(dppe)] (dppe = 1,2-bis(diphenyphosphanyl)ethane) as catalyst by 1 H and 13 C NMR spectroscopy.…”

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confidence: 99%

Effective Fixation of CO₂ by Iridium‐Catalyzed Hydrosilylation

et al. 2012

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“…[1] In the case of ketones and imines, it also serves as a convenient reduction method in that it provides protected alcohols and amines in one step. [2] Whereas diverse procedures have been developed for the hydrosilylation of C = X (X = C, N, O), [1] P = O, [3] S = O, [4] and CC bonds, [1,5] SiÀH addition to the NC triple bond remains a great synthetic challenge.…”

mentioning

confidence: 99%