JP2016518322A - 不斉転換のための有機金属の触媒作用 - Google Patents
不斉転換のための有機金属の触媒作用 Download PDFInfo
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Abstract
Description
本出願は、2013年3月11日に提出された米国仮出願番号第61/775,807号に対して米国特許法第119条(e)項に基づく利益を主張するものであり、当該出願の開示は、全体として参照により本明細書中に組み込まれる。
特異な活性化モードを伴う遷移金属触媒作用および有機触媒作用において、非常に多くの優れた触媒が開発されてきている。しかしながら、かような触媒の利用は、反応の範囲が限られていることや、触媒量が多いといった固有の欠点により妨げられている。これらの制限を改善する試みにおいて、近年、遷移金属触媒作用と有機触媒作用とを組み合わせるという構想が浮上している。共同触媒作用、相乗的触媒作用、および連続した/リレー触媒作用といった方策が確立されている。しかしながら、触媒、基質、中間体および溶媒の間の不和合性が潜在的な欠点となっている。
本明細書は、以下の構造またはそのエナンチオマーを有する配位子を開示する:
本明細書は、キラルなビスホスフィンが有機触媒と共有結合により結合することにより、個々の金属触媒および有機触媒と比較して、転化率および選択性が顕著に改善された配位子および当該配位子から調製される触媒を開示する。ビスホスフィンと錯形成した金属は、一般的な触媒であり、高い回転数で、多くの金属触媒反応を促進することができる。有機触媒は、基質を活性化し、選択性に影響を与える。本明細書中に用いられる「有機金属の触媒作用」の用語は、有機触媒部分と共有結合的に結合した金属触媒部分を有する化合物により、触媒される反応およびその触媒を指す。金属部分に由来する高い活性および有機触媒に由来する高い選択性により、不斉触媒における有用な手法が提供される。
「アルキル」の用語は、直鎖のアルキル基および分岐のアルキル基を含む、飽和の脂肪族基のラジカルをいう。「シクロアルキル」の用語は、炭素原子数が約3〜7である非芳香族の単環式または多環式環系をいう。シクロアルキル基の例としては、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル等が挙げられる。
材料および方法
空気または湿気に敏感な化合物を扱う反応は、乾燥容器中、窒素加圧の下、または窒素で満たされたグローブボックス中で行った。他に記載のない限り、すべての試薬および溶媒は、商業用の供給者から購入し、さらに精製は行わなかった。無水溶媒は、シグマ−アルドリッチから購入し、シリンジによって導入した。生成物の精製は、ACROS社製シリカゲル(0.06−0.20mm)を用いたクロマトグラフィーにより行い、分析薄層クロマトグラフィー(TLC)は、Merck社製シリカゲルプレート(GF254)を用いて行った。[Rh(COD)Cl]2、[Rh(COD)2]BF4および[Rh(COD)2]SbF6は、Heraeusから購入した。HPLC溶媒は、Alfa(n−ヘキサン)およびシグマ−アルドリッチ(2−プロパノール)から購入した。
すべてのN−Hイミンは、文献(Hou, G., et al., J. Am. Chem. Soc. 2009, 131, 9882-9883.)に従って調製した。すべてのスペクトルデータは、文献の値と一致した。
Claims (16)
- 以下の構造またはそのエナンチオマーを有する配位子:
Ra、Rb、Rc、およびRdは、それぞれ独立して、アルキル、シクロアルキル、およびアリールからなる群から選択され;
架橋基は、CH2NH;*CH(CH3)NH(C*,R);および*CH(CH3)NH(C*,S)からなる群から選択され;かつ
有機触媒は、前記架橋基に共有結合的に結合した有機分子触媒である。 - Ra、Rb、Rc、およびRdのうち少なくとも一つは、フェニル;P−CH3フェニル;3,5−ジ−CH3フェニル;3,5−ジ−t−ブチルフェニル;3,5−ジ−CF3フェニル;2−CH3フェニル;C6F5;2−ナフチル;および1−ナフチルからなる群から選択されるアリール部分である、請求項1に記載の配位子。
- Ra、Rb、Rc、およびRdのうち少なくとも一つは、t−ブチルおよびi−プロピルからなる群から選択されるアルキル部分である、請求項1に記載の配位子。
- Ra、Rb、Rc、およびRdのうち少なくとも一つは、シクロヘキシルおよびシクロペンチルからなる群から選択されるシクロアルキル部分である、請求項1に記載の配位子。
- 以下の式によって表される化合物からなる群から選択される、請求項1に記載の配位子:
- 以下の式によって表される化合物からなる群から選択される、請求項1に記載の配位子:
- 以下の式によって表される化合物からなる群から選択される、請求項1に記載の配位子:
- 以下の構造またはそのエナンチオマーを有する触媒:
Ra、Rb、Rc、およびRdは、それぞれ独立して、アルキル、シクロアルキル、およびアリールからなる群から選択され;
架橋基は、CH2NH;*CH(CH3)NH(C*,R);および*CH(CH3)NH(C*,S)からなる群から選択され;
有機触媒は、前記架橋基に共有結合的に結合した有機分子触媒であり;かつ
Mは、Rh、Pd、Cu、Ru、Ir、Ag、Au、Zn、Ni、Co、およびFeからなる群から選択される。 - Ra、Rb、Rc、およびRdのうち少なくとも一つは、フェニル;P−CH3フェニル;3,5−ジ−CH3フェニル;3,5−ジ−t−ブチルフェニル;3,5−ジ−CF3フェニル;2−CH3フェニル;C6F5;2−ナフチル;および1−ナフチルからなる群から選択されるアリール部分である、請求項8に記載の触媒。
- Ra、Rb、Rc、およびRdのうち少なくとも一つは、t−ブチルおよびi−プロピルからなる群から選択されるアルキル部分である、請求項8に記載の触媒。
- Ra、Rb、Rc、およびRdのうち少なくとも一つは、シクロヘキシルおよびシクロペンチルからなる群から選択されるシクロアルキル部分である、請求項8に記載の触媒。
- アルケンを水素化するために有効な温度および圧力下で、適当な溶媒中、前記アルケンを、過剰量の水素ガスおよび触媒的に有効な量の請求項8に記載の触媒と混合することを含む、アルケンを対応するアルカンに不斉水素化する方法。
- 前記溶媒は、イソプロパノールを含む、請求項12に記載の方法。
- 前記触媒中のRa、Rb、Rc、およびRdのうち少なくとも一つは、フェニル;P−CH3フェニル;3,5−ジ−CH3フェニル;3,5−ジ−t−ブチルフェニル;3,5−ジ−CF3フェニル;2−CH3フェニル;C6F5;2−ナフチル;および1−ナフチルからなる群から選択されるアリール部分である、請求項12に記載の方法。
- 前記触媒中のRa、Rb、Rc、およびRdのうち少なくとも一つは、t−ブチルおよびi−プロピルからなる群から選択されるアルキル部分である、請求項12に記載の方法。
- 前記触媒中のRa、Rb、Rc、およびRdのうち少なくとも一つは、シクロヘキシルおよびシクロペンチルからなる群から選択されるシクロアルキル部分である、請求項12に記載の方法。
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