Precatalyst for shibasaki's rare earth metal binolate catalysts

Patent metadata

Field	Value
Publication number	US-2016145273-A1
Application number	US-201414898925-A
Country	US
Kind code	A1
Filing date	Jun 23, 2014
Priority date	Jun 21, 2013
Publication date	May 26, 2016
Grant date	—

Abstract

Disclosed herein are schemes for the synthesis of novel hydrogen-bonded rare earth-BINOLate precatalyst complexes, the precatalysts, per se, and their application for the generation of anhydrous REMB catalysts by cation-exchange from metal halides.

First claim

1 . A precatalyst complex of the formula:

wherein RE represents a rare earth element, NR n represents an amine base, m=1 or 2, n=1, 2 or 3 and m+n≦4; and the dashed lines indicate hydrogen bonding which may be monodentate or bidentate hydrogen bonding.

2 . The precatalyst of claim 1 , wherein RE is a rare earth element selected from Sc, Y and La through Lu.

3 . The precatalyst of claim 1 , wherein the amine base is selected from the group of a guanidine, an amidine and a heterocyclic amine, said amidine being cyclic or non-cyclic.

4 . A process for preparing the precatalyst complex of claim 1 by forming a reaction mixture comprising (i) a rare earth-containing reactant selected from the group of RE(NO 3 ) 3 , RE(N[SiMe 3 ] 2 ); (ii) (S)1,1′-bi-2-naphthol((S)-BINOL) and (iii) NR 3 in a suitable solvent, and subjecting said mixture to conditions yielding said complex.

5 . A process for generating a REMB catalyst comprising reacting the precatalyst complex of claim 1 with a metal halide or a pseudo-halide to yield said REMB catalyst.

6 . The process of claim 5 , wherein said metal halide is an alkali metal halide.

7 . The process of claim 5 , wherein said pseudo-halide comprises an alkali metal cation and an anion selected from the group of tetrafluoroborate, hexafluorophosphate, tetrakis-(3,5-bis(trifluoromethyl)) borate.

8 . A process for generating a REMB catalyst comprising reacting the precatalyst complex of claim 1 with M(N[SiMe 3 ] 2 ), M being an alkali metal, to yield said REMB catalyst.

9 . The catalyst produced by the process of claim 5 .

10 . In a chemical reaction comprising the base-promoted conjugate addition of a carbon nucleophile/donor to an activated, unsaturated compound/acceptor, the improvement which comprises catalyzing said reaction using the catalyst of claim 9 .

11 . In a chemical reaction comprising the 1,4-addition of a dienophile double bond to a conjugated dien to yield a 6-membered ring compound having at least one chiral center, the improvement which comprises catalyzing said reaction using the catalyst of claim 9 .

12 . A catalyzed chemical reaction selected from the group of a Michael addition reaction, an aza-Michael addition reaction and a direct Aldol reaction, wherein the catalyst in the reaction is generated from the precatalyst of claim 1 .

Assignees

• Univ Pennsylvania

Inventors

• Walsh Patrick
• Schelter Eric J
• Robinson Jerome

Classifications

• C07D333/22

  Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom · CPC title

• C07B37/02

  Addition · CPC title

• C07C45/61

  by reactions not involving the formation of >C = O groups · CPC title

• B01J31/2213

  At least two complexing oxygen atoms present in an at least bidentate or bridging ligand · CPC title

• C07B53/00

  Asymmetric syntheses · CPC title