TOP > 外国特許検索 > Process of making alpha-aminooxyketone/alpha-aminooxyaldehyde and alpha-hydroxyketone/alpha-hydroxyaldehyde compounds and a process making reaction products from cyclic alpha, beta-unsaturated ketone substrates and nitroso substrates

Process of making alpha-aminooxyketone/alpha-aminooxyaldehyde and alpha-hydroxyketone/alpha-hydroxyaldehyde compounds and a process making reaction products from cyclic alpha, beta-unsaturated ketone substrates and nitroso substrates

外国特許コード F110005360
整理番号 B12-03US
掲載日 2011年9月5日
出願国 アメリカ合衆国
出願番号 57883609
公報番号 20100099915
公報番号 8252941
出願日 平成21年10月14日(2009.10.14)
公報発行日 平成22年4月22日(2010.4.22)
公報発行日 平成24年8月28日(2012.8.28)
国際出願番号 US2005005426
国際公開番号 WO2005090294
国際出願日 平成17年2月18日(2005.2.18)
国際公開日 平成17年9月29日(2005.9.29)
優先権データ
  • 特願2004-044540 (2004.2.20) JP
  • 2004US-60564048 (2004.4.20) US
  • 2005WO-US05426 (2005.2.18) WO
  • 2006US-11506590 (2006.10.25) US
発明の名称 (英語) Process of making alpha-aminooxyketone/alpha-aminooxyaldehyde and alpha-hydroxyketone/alpha-hydroxyaldehyde compounds and a process making reaction products from cyclic alpha, beta-unsaturated ketone substrates and nitroso substrates
発明の概要(英語) (US8252941)
The present invention is directed to a process of making α-aminooxyketone and α-hydroxyketone compounds.
The synthetic pathway generally involves reacting an aldehyde or ketone substrate and a nitroso substrate in the presence of a catalyst of the formula (IV): wherein Xa―Xc represent independently nitrogen, carbon, oxygen or sulfur and Z represents a 4 to 10-membered ring with or without a substituent and optionally a further step to convert the α-aminooxyketone compound formed to the α-hydroxyketone compound.
The present invention results in α-aminooxyketone and α-hydroxyketone compounds with high enantioselectivity and high purity.
The present invention is also directed to a catalytic asymmetric O-nitroso Aldol/Michael reaction.
The substrates of this reaction are generally cyclic α,β-unsaturated ketone substrate and a nitroso substrate.
This methodology generally involves reacting the cyclic α,β-unsaturated ketone substrate and the nitroso substrate in the presence of a proline-based catalyst, to provide a heterocyclic product.
特許請求の範囲(英語) [claim1]
1. A process of making an enantioenriched alpha -aminooxyketone comprising reacting a ketone of formula (II):
with a nitroso compound of formula (IIIa) or (IIIb):
in the presence of a solvent and a catalyst of formula (IVa):
wherein:
R1 and R2 independently represent either hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted alkoxycarbonyl group; a substituted or unsubstituted aryl group; or
R1 and R2 together form a cycloalkyl ring;
R3 is each independently selected from the group consisting of:
hydrogen, halogen, -- OR5, -- OC(O)R5, -- CN, -- C(O)R5, -- CO2R5, -- C(O)NR5R5', -- NO2, -- NR5R5', -- NRC(O)R5, -- NR5CO2R5', -- NR5S(O)2R5', -- SR5, -- S(O)R5, -- S(O)2R5, -- S(O)2NR5R5', C1-8 alkyl, C2-8 alkenyl, C2-8 alkynyl, C3-8 cycloalkyl, C6-10 aryl, 5- to 10-membered heteroaryl, and 3- to 10-membered heterocyclyl; wherein each R5 and R5' may be independently selected from the group consisting of hydrogen, C1-8 alkyl, C2-8 alkenyl, C2-8 alkynyl, C3-8 cycloalkyl, C6-10 aryl, 5- to 10-membered heteroaryl, and 3- to 10-membered heterocyclyl;
n is an integer from 0-5;
R4 is substituted or unsubstituted alkyl;
the configuration of the stereogenic carbon alpha to the nitrogen on the pyrolidine ring is the (L) or optionally (D) configuration.
[claim2]
2. The process of claim 1 wherein: R1 and R2 independently represent either hydrogen; a substituted or unsubstituted C1-C8 alkyl group; a substituted or unsubstituted C1-C8 alkoxy group; a substituted or unsubstituted C1-C8 alkoxycarbonyl group; a substituted or unsubstituted aryl group, wherein the groups when substituted are substituted by the group consisting of hydrogen, halogen, -- OR4, -- OC(O)R4, -- CN, -- C(O)R4, -- CO2R4, -- C(O)NR4R5, -- NO2, -- NR4R5, -- NRC(O)R4, -- NR4CO2R5, -- NR4S(O)2R5, -- SR4, -- S(O)R4, -- S(O)2R4, -- S(O)2NR4R5, C1-8 alkyl, C3-8 cycloalkyl, C6-10 aryl, 5- to 10-membered heteroaryl, and 3- to 10-membered heterocyclyl; or
R1 and R2 together form a C3-C8 cycloalkyl ring;
R3 is each independently selected from the group consisting of: hydrogen, halogen, -- OR5, -- OC(O)R5, -- CN, -- C(O)R5, -- CO2R5, -- C(O)NR5R5', -- NO2, -- NR5R5', -- NRC(O)R5, -- NR5CO2R5', -- NR5S(O)2R5', -- SR5, -- S(O)R5, -- S(O)2R5, -- S(O)2NR5R5', C1-8 alkyl, C2-8 alkenyl, C2-8 alkynyl, C3-8 cycloalkyl, C6-10 aryl, 5- to 10-membered heteroaryl, and 3- to 10-membered heterocyclyl; wherein each R5 and R5' may be independently selected from the group consisting of hydrogen, C1-8 alkyl, C2-8 alkenyl, C2-8 alkynyl, C3-8 cycloalkyl, C6-10 aryl, 5- to 10-membered heteroaryl, and 3- to 10-membered heterocyclyl;
R4 is a substituted or unsubstituted C1-C8 alkyl, wherein when substituted are substituted by the group consisting of halogen, -- OR5, -- OC(O)R5, -- CN, -- C(O)R5, -- CO2R5, -- C(O)NR5R5', -- NO2, -- NR5R5', -- NRC(O)R5, -- NR5CO2R5', -- NR5S(O)2R5', -- SR5, -- S(O)R5, -- S(O)2R5, -- S(O)2NR5R5', C1-8 alkyl, C2-8 alkenyl, C2-8 alkynyl, C3-8 cycloalkyl, C6-10 aryl, 5- to 10-membered heteroaryl, and 3- to 10-membered heterocyclyl; wherein each R5 and R5' may be independently selected from the group consisting of hydrogen, C1-8 alkyl, C2-8 alkenyl, C2-8 alkynyl, C3-8 cycloalkyl, C6-10 aryl, 5- to 10-membered heteroaryl, and 3- to 10-membered heterocyclyl;
n is an interger from 0-3; and
the configuration of the stereogenic carbone alpha to the nitrogen on the pyrolidine ring is the (L) or optionally (D) configuration.
[claim3]
3. The process of claim 1 wherein the enantioselectivity is greater than 99% enantiomeric excess (ee).
[claim4]
4. The process of claim 1 wherein the catalyst has the following structure:
  • 発明者/出願人(英語)
  • MOMIYAMA NORIE
  • TORII HIROMI
  • SAITO SUSUMU
  • YAMAMOTO HISASHI
  • YAMAMOTO YUHEI
  • JAPAN SCIENCE AND TECHNOLOGY AGENCY
国際特許分類(IPC)
米国特許分類/主・副
  • C07C291/04
  • C07D207/16
  • C07D211/74
  • C07D309/30
  • C07D317/72
  • C07D403/04
  • M07C101/14
参考情報 (研究プロジェクト等) SORST Selected in Fiscal 2000
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