[Phosferrox]-Ru

In situ generated catalyst utilised first by Sammakia [JOC97-62-6104] and Hou [CJC98-16-117]. Isolated catalyst prepared by Uemura [JOMC99-572-163].

C46H43Cl2FeNOP2Ru_1

Ru – Transfer hydrogenation Orgmet99-18-2291

PN-L1a_b_Transfer_hydrog_C

Method also applied to the reduction of alkyl methyl ketones RCOMe with opposite S enantioselection (R = t-Bu >99% ee, R = Cy 66% ee, R = n-hexyl 26% ee). The example of the representative reaction, under the same conditions, has been reported to give 96% ee, 99% conversion, see: Orgmet12-31-4241.

 

Ru – Oxidative kinetic resolution Orgmet99-18-2291

PN-L1a_b_Oxidative-kinetic-

JOC03-68-5875

PN-L1a_b_Oxidative-kinetic-B-1

 

Ru – Reductive alkylation Angew06-45-3819

A one-pot sequential sequence also requiring [IrCl(COD)]2.

PN-L1a_b_Reductive-alk

 

Ru – Deracemisation AJC07-2-393

A one-pot sequential sequence also requiring [RuCl{(S,S)-tsdpen)(η6-mesitylene)].

PN-L1a_b_Deracemisation

 

Ru – Hydrogenation 

Both in situ generated and isolated [(S,Sp)-PN-L1a]RuCl2(PPh3) have been applied to hydrogenation with essentially identical results. An induction time has been reported on use of the isolated complex. In contrast to transfer hydrogenation, significant rate enhancements are possible by increasing the pressure of H2.

ASC06-348-47

hydrogenation

OPRD07-11-519

hydrogenation_A

TA06-17-550 

hydrogenation_B

TA07-18-2381

hydrogenation_C

 

Ru – Hydrosilylation Orgmet98-17-3421

PN-L1a_b_Hydrosilylation

CC01-2360

PN-L1a_b_Hydrosilylation_B