Asymmetric Synthesis of (Triaryl)methylamines by Rhodium-Catalyzed Addition of Arylboroxines to Cyclic <i>N</i>-Sulfonyl Ketimines

Nishimura, Takahiro; Noishiki, Akira; Tsui, Gavin Chit; Hayashi, Tamio

doi:10.1021/ja300697c

Cited by 221 publications

(79 citation statements)

References 75 publications

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“…A green 255,256 and highly enantioselective micellar catalytic strategy for the 1,4-addition of differently substituted arylboronic acids 2 to cyclic ketones 1a-c,g affording chiral ketones 263a-l in high chemical yields and with high enantioselectivities mediated by either SDS or PTS as surfactants has achieved and reported (Table 85). 257 The reactions occur in water as the sole solvent at ambient temperature. Such transformations normally occur in organic solvents and require harsh reaction conditions.…”

Section: Table 48mentioning

confidence: 99%

Rh-catalyzed asymmetric 1,4-addition reactions to α,β-unsaturated carbonyl and related compounds: an update

Heravi

Dehghani

Zadsirjan

2016

Tetrahedron: Asymmetry

109

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Rh-catalyzed asymmetric 1,4-addition reactions to a,b-unsaturated carbonyl and related compounds: an update Available online xxxx Dedicated to my son, OMID on the occasion of his 35th birthday. a b s t r a c tThe Rh-catalyzed asymmetric 1,4-addition of organometallic reagents to an appropriate receptor has been a growing area of research over the last decade. The receptors for such a 1,4-addition reaction are chiefly a,b-unsaturated ketones, esters, amides, enones, nitroalkenes, and occasionally phosphonates etc. This reaction in the presence of chiral rhodium complexes introduce the aryl and alkenyl groups at the b-position of the above electron poor olefins, enantioselectively. Chiral Rh complexes similar to other transition metals can be added to some electron poor olefins, in turn making them viable to attack by various organometallic reagents for highly enantioselective C-C bond formation. The Rh-catalyzed asymmetric 1,4-addition of organometallic reagents to electron poor olefins has been reviewed in 2003. Due to the importance of the asymmetric C-C bond formation via 1,4-conjugate addition reactions and the number of such reactions catalyzed by Rh-complexes, in this review we highlight the recent advances in Rh-complex asymmetric catalyzed 1,4-addition reactions since 2003.

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Section: Table 48mentioning

confidence: 99%

Rh-catalyzed asymmetric 1,4-addition reactions to α,β-unsaturated carbonyl and related compounds: an update

Heravi

Dehghani

Zadsirjan

2016

Tetrahedron: Asymmetry

109

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“…The C=N endocyclic N-sulfonylketimine 30 served as a suitable electrophile, which was used in combination with arylboroxine 31. 26,27 Ligand screening including chiral bisphosphine ligands established that the Rh complex prepared from chiral diene ligand 26 performed the best; the use of this catalytic system afforded arylated product 33 in high yield and enantioselectivity (Scheme 9a). 28 Coordination of the ketimine through the Re-face to Ar-Rh species in a η 2 -fashion was proposed to explain the obtained stereochemistry.…”

Section: C=n Endocyclic Ketiminesmentioning

confidence: 99%

Recent Advances in Catalytic Asymmetric C–C Bond-Forming Reactions to Ketimines Promoted by Metal-Based Catalysts

Kumagai

Shibasaki

2014

Bulletin of the Chemical Society of Japan

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Recent progress (post-2010) in the field of metal-catalyzed asymmetric CC bond-forming reactions using ketimines as electrophiles is reviewed. Compared with the corresponding aldimines, ketimines generally display less inherent reactivity and the two substituents on the imine carbon hamper prochiral-face-selection for enantioselective reactions. Recent advances with newly developed catalytic systems have resulted in several solutions to these long-standing problems. The construction of tetrasubstituted stereogenic centers is a crucial topic of asymmetric catalysis in the 21st century, and it is becoming increasingly clear that reactions using ketimines as electrophiles become one of the most important routes to access such chemical entities.

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“…Methods involving non-stabilized nucleophiles remain significantly underdeveloped, with only a few reports to date. The main advances in this area have been achieved in the field of Rh- and Pd-catalysed addition of Csp 2 -nucleophiles to N -sulfonyl ketimines using boron reagents567. However, the addition of Csp 3 -nucleophiles is restricted to methylations and ethylations of a small set of ketimines using organozinc or organoaluminium reagents with Cu, Zr or Rh catalysts8910.…”

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confidence: 99%

Catalytic enantioselective addition of Grignard reagents to aromatic silyl ketimines

et al. 2016

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α-Chiral amines are of significant importance in medicinal chemistry, asymmetric synthesis and material science, but methods for their efficient synthesis are scarce. In particular, the synthesis of α-chiral amines with the challenging tetrasubstituted carbon stereocentre is a long-standing problem and catalytic asymmetric additions of organometallic reagents to ketimines that would give direct access to these molecules are underdeveloped. Here we report a highly enantioselective catalytic synthesis of N-sulfonyl protected α-chiral silyl amines via the addition of inexpensive, easy to handle and readily available Grignard reagents to silyl ketimines. The key to this success was our ability to suppress any unselective background addition reactions and side reduction pathway, through the identification of an inexpensive, chiral Cu-complex as the catalytically active structure.

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Asymmetric Synthesis of (Triaryl)methylamines by Rhodium-Catalyzed Addition of Arylboroxines to Cyclic N-Sulfonyl Ketimines

Cited by 221 publications

References 75 publications

Rh-catalyzed asymmetric 1,4-addition reactions to α,β-unsaturated carbonyl and related compounds: an update

Rh-catalyzed asymmetric 1,4-addition reactions to α,β-unsaturated carbonyl and related compounds: an update

Recent Advances in Catalytic Asymmetric C–C Bond-Forming Reactions to Ketimines Promoted by Metal-Based Catalysts

Catalytic enantioselective addition of Grignard reagents to aromatic silyl ketimines

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