Catalytic asymmetric heterogeneous aziridination using CuHY/bis(oxazoline): effect of reaction conditions on enantioselectivity

Sophia Taylor; John Gullick; Natasha Galea; Paul McMorn; Donald Bethell; Philip C. Bulman Page; Frederick E. Hancock; Frank King; David J. Willock; Graham J. Hutchings

doi:10.1023/B:TOCA.0000003100.56246.39

Catalytic asymmetric heterogeneous aziridination using CuHY/bis(oxazoline): effect of reaction conditions on enantioselectivity

Sophia Taylor, John Gullick, Natasha Galea, Paul McMorn, Donald Bethell, Philip C. Bulman Page, Frederick E. Hancock, Frank King, David J. Willock, Graham J. Hutchings

Chemistry of Materials and Catalysis

Research output: Contribution to journal › Article › peer-review

Abstract

The copper-catalyzed aziridination of styrene with copper-exchanged zeolite HY(CuHY) and copper(II) triflate (trifluoromethanesulfonate) (Cu(OTf)(2)) as catalysts is described using N-(p-tolylsulfonyl) imino] phenyliodinane (PhI=NTs) as the nitrene donor. The effects on the ee and yield of the aziridine when the catalyst is modified by the presence of a chiral bis(oxazoline) are investigated in detail. The heterogeneously catalyzed reaction under these conditions shows a slight, but significant, enhancement in ee with increasing conversion at 25degreesC. This is not observed in the more rapid homogeneously catalyzed reaction under identical reaction conditions using PhINTs as the nitrene donor. The enhancement in ee is proposed to result from the preferential reaction of the (S)-aziridine with the Cu2+:bis(oxazoline) complex in the presence of PhI=NTs, leading to an enhancement of the (R)-aziridine in the remaining aziridine product.

Original language	English
Pages (from-to)	81-88
Number of pages	8
Journal	Topics in Catalysis
Volume	25
Issue number	1-4
DOIs	https://doi.org/10.1023/B:TOCA.0000003100.56246.39
Publication status	Published - 2003

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10.1023/B:TOCA.0000003100.56246.39

Cite this

@article{b7e09f03379049b38ee243bb51ded6d9,

title = "Catalytic asymmetric heterogeneous aziridination using CuHY/bis(oxazoline): effect of reaction conditions on enantioselectivity",

abstract = "The copper-catalyzed aziridination of styrene with copper-exchanged zeolite HY(CuHY) and copper(II) triflate (trifluoromethanesulfonate) (Cu(OTf)(2)) as catalysts is described using N-(p-tolylsulfonyl) imino] phenyliodinane (PhI=NTs) as the nitrene donor. The effects on the ee and yield of the aziridine when the catalyst is modified by the presence of a chiral bis(oxazoline) are investigated in detail. The heterogeneously catalyzed reaction under these conditions shows a slight, but significant, enhancement in ee with increasing conversion at 25degreesC. This is not observed in the more rapid homogeneously catalyzed reaction under identical reaction conditions using PhINTs as the nitrene donor. The enhancement in ee is proposed to result from the preferential reaction of the (S)-aziridine with the Cu2+:bis(oxazoline) complex in the presence of PhI=NTs, leading to an enhancement of the (R)-aziridine in the remaining aziridine product.",

author = "Sophia Taylor and John Gullick and Natasha Galea and Paul McMorn and Donald Bethell and {Bulman Page}, {Philip C.} and Hancock, {Frederick E.} and Frank King and Willock, {David J.} and Hutchings, {Graham J.}",

year = "2003",

doi = "10.1023/B:TOCA.0000003100.56246.39",

language = "English",

volume = "25",

pages = "81--88",

journal = "Topics in Catalysis",

issn = "1022-5528",

publisher = "Springer",

number = "1-4",

}

TY - JOUR

T1 - Catalytic asymmetric heterogeneous aziridination using CuHY/bis(oxazoline): effect of reaction conditions on enantioselectivity

AU - Taylor, Sophia

AU - Gullick, John

AU - Galea, Natasha

AU - McMorn, Paul

AU - Bethell, Donald

AU - Bulman Page, Philip C.

AU - Hancock, Frederick E.

AU - King, Frank

AU - Willock, David J.

AU - Hutchings, Graham J.

PY - 2003

Y1 - 2003

N2 - The copper-catalyzed aziridination of styrene with copper-exchanged zeolite HY(CuHY) and copper(II) triflate (trifluoromethanesulfonate) (Cu(OTf)(2)) as catalysts is described using N-(p-tolylsulfonyl) imino] phenyliodinane (PhI=NTs) as the nitrene donor. The effects on the ee and yield of the aziridine when the catalyst is modified by the presence of a chiral bis(oxazoline) are investigated in detail. The heterogeneously catalyzed reaction under these conditions shows a slight, but significant, enhancement in ee with increasing conversion at 25degreesC. This is not observed in the more rapid homogeneously catalyzed reaction under identical reaction conditions using PhINTs as the nitrene donor. The enhancement in ee is proposed to result from the preferential reaction of the (S)-aziridine with the Cu2+:bis(oxazoline) complex in the presence of PhI=NTs, leading to an enhancement of the (R)-aziridine in the remaining aziridine product.

AB - The copper-catalyzed aziridination of styrene with copper-exchanged zeolite HY(CuHY) and copper(II) triflate (trifluoromethanesulfonate) (Cu(OTf)(2)) as catalysts is described using N-(p-tolylsulfonyl) imino] phenyliodinane (PhI=NTs) as the nitrene donor. The effects on the ee and yield of the aziridine when the catalyst is modified by the presence of a chiral bis(oxazoline) are investigated in detail. The heterogeneously catalyzed reaction under these conditions shows a slight, but significant, enhancement in ee with increasing conversion at 25degreesC. This is not observed in the more rapid homogeneously catalyzed reaction under identical reaction conditions using PhINTs as the nitrene donor. The enhancement in ee is proposed to result from the preferential reaction of the (S)-aziridine with the Cu2+:bis(oxazoline) complex in the presence of PhI=NTs, leading to an enhancement of the (R)-aziridine in the remaining aziridine product.

U2 - 10.1023/B:TOCA.0000003100.56246.39

DO - 10.1023/B:TOCA.0000003100.56246.39

M3 - Article

VL - 25

SP - 81

EP - 88

JO - Topics in Catalysis

JF - Topics in Catalysis

SN - 1022-5528

IS - 1-4

ER -