Sulfoxide ligand metal catalyzed oxidation of olefins

M Christina White; Stephen E Ammann; Wei Liu; Rulin Ma

Sulfoxide ligand metal catalyzed oxidation of olefins

M Christina White (Inventor), Stephen E Ammann (Inventor), Wei Liu (Inventor), Rulin Ma (Inventor)

Research output: Patent

Abstract

The enantioselective synthesis of isochroman motifs has been accomplished via Pd(II)-catalyzed allylic C—H oxidation from terminal olefin precursors. Critical to the success of this goal was the development and utilization of a novel chiral aryl sulfoxide-oxazoline (ArSOX) ligand. The allylic C—H oxidation reaction proceeds with the broadest scope and highest levels asymmetric induction reported to date (avg. 92' ee, 13 examples ≥90' ee). Additionally, C(sp3)-N fragment coupling reaction between abundant terminal olefins and N-triflyl protected aliphatic and aromatic amines via Pd(II)/sulfoxide (SOX) catalyzed intermolecular allylic C—H amination is disclosed. A range of 52 allylic amines are furnished in good yields (avg. 76') and excellent regio- and stereoselectivity (avg. >20:1 linear:branched, >20:1 E:Z). For the first time, a variety of singly activated aromatic and aliphatic nitrogen nucleophiles, including ones with stereochemical elements, can be used in fragment coupling stiochiometries for intermolecular C—H amination reactions.

Original language	English (US)
U.S. patent number	10266503
Filing date	5/24/17
State	Published - Apr 23 2019

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title = "Sulfoxide ligand metal catalyzed oxidation of olefins",

abstract = "The enantioselective synthesis of isochroman motifs has been accomplished via Pd(II)-catalyzed allylic C—H oxidation from terminal olefin precursors. Critical to the success of this goal was the development and utilization of a novel chiral aryl sulfoxide-oxazoline (ArSOX) ligand. The allylic C—H oxidation reaction proceeds with the broadest scope and highest levels asymmetric induction reported to date (avg. 92' ee, 13 examples ≥90' ee). Additionally, C(sp3)-N fragment coupling reaction between abundant terminal olefins and N-triflyl protected aliphatic and aromatic amines via Pd(II)/sulfoxide (SOX) catalyzed intermolecular allylic C—H amination is disclosed. A range of 52 allylic amines are furnished in good yields (avg. 76') and excellent regio- and stereoselectivity (avg. >20:1 linear:branched, >20:1 E:Z). For the first time, a variety of singly activated aromatic and aliphatic nitrogen nucleophiles, including ones with stereochemical elements, can be used in fragment coupling stiochiometries for intermolecular C—H amination reactions.",

author = "White, {M Christina} and Ammann, {Stephen E} and Wei Liu and Rulin Ma",

note = "GOVERNMENT SUPPORT This invention was made with government support under Grant No. 2RO1 GM076153B awarded by the National Institutes of Health. The government has certain rights in the invention.; 10266503",

year = "2019",

month = apr,

day = "23",

language = "English (US)",

type = "Patent",

}

TY - PAT

T1 - Sulfoxide ligand metal catalyzed oxidation of olefins

AU - White, M Christina

AU - Ammann, Stephen E

AU - Liu, Wei

AU - Ma, Rulin

N1 - GOVERNMENT SUPPORT This invention was made with government support under Grant No. 2RO1 GM076153B awarded by the National Institutes of Health. The government has certain rights in the invention.

PY - 2019/4/23

Y1 - 2019/4/23

N2 - The enantioselective synthesis of isochroman motifs has been accomplished via Pd(II)-catalyzed allylic C—H oxidation from terminal olefin precursors. Critical to the success of this goal was the development and utilization of a novel chiral aryl sulfoxide-oxazoline (ArSOX) ligand. The allylic C—H oxidation reaction proceeds with the broadest scope and highest levels asymmetric induction reported to date (avg. 92' ee, 13 examples ≥90' ee). Additionally, C(sp3)-N fragment coupling reaction between abundant terminal olefins and N-triflyl protected aliphatic and aromatic amines via Pd(II)/sulfoxide (SOX) catalyzed intermolecular allylic C—H amination is disclosed. A range of 52 allylic amines are furnished in good yields (avg. 76') and excellent regio- and stereoselectivity (avg. >20:1 linear:branched, >20:1 E:Z). For the first time, a variety of singly activated aromatic and aliphatic nitrogen nucleophiles, including ones with stereochemical elements, can be used in fragment coupling stiochiometries for intermolecular C—H amination reactions.

AB - The enantioselective synthesis of isochroman motifs has been accomplished via Pd(II)-catalyzed allylic C—H oxidation from terminal olefin precursors. Critical to the success of this goal was the development and utilization of a novel chiral aryl sulfoxide-oxazoline (ArSOX) ligand. The allylic C—H oxidation reaction proceeds with the broadest scope and highest levels asymmetric induction reported to date (avg. 92' ee, 13 examples ≥90' ee). Additionally, C(sp3)-N fragment coupling reaction between abundant terminal olefins and N-triflyl protected aliphatic and aromatic amines via Pd(II)/sulfoxide (SOX) catalyzed intermolecular allylic C—H amination is disclosed. A range of 52 allylic amines are furnished in good yields (avg. 76') and excellent regio- and stereoselectivity (avg. >20:1 linear:branched, >20:1 E:Z). For the first time, a variety of singly activated aromatic and aliphatic nitrogen nucleophiles, including ones with stereochemical elements, can be used in fragment coupling stiochiometries for intermolecular C—H amination reactions.

M3 - Patent

M1 - 10266503

Y2 - 2017/05/24

ER -

Sulfoxide ligand metal catalyzed oxidation of olefins

Abstract

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