Reactivity of (bicyclo[5.1.0]octadienyl)iron(1+) cations: application to the synthesis of cis-2-(2'-carboxycyclopropyl)glycines.
Reactivity of (bicyclo[5.1.0]octadienyl)iron(1+) cations: application to the synthesis of cis-2-(2'-carboxycyclopropyl)glycines.
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(双环[5.1.0]辛二烯基)铁(1)阳离子的反应性：应用于顺式-2-(2-羧基环丙基)甘氨酸的合成。
DOI：
10.1021/jo030259a
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发表时间：
2004
期刊：
影响因子：
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通讯作者：
Donaldson,WilliamA
中科院分区：
文献类型：
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作者：
Wallock,NathanielJ;Donaldson,WilliamA
碳和杂原子亲核试剂与（双环[5.1.0]辛二烯基）Fe（CO）2L+阳离子5或8（L = CO，PPh 3）的加成通常通过在配体与铁相对的面上的二烯基末端进攻进行，生成6-取代的（双环[5.1.0]辛-2，4-二烯）铁络合物（11或13）。在某些情况下，这些产物在质子和亲核取代基的消除方面是不稳定的，从而得到（环辛四烯）Fe（CO）2L（4或7）。邻苯二甲酰亚胺加成到8上产生的13 f的解络合得到N-（双环[5.1.0]辛-3，5-二烯-2-基）邻苯二甲酰亚胺（19）。19的氧化裂解（RuCl 3/NaIO 4）接着酯化得到环丙烷二酯22，其在水解时得到顺式-2-（2 '-羧基环丙基）甘氨酸（CCG-III，18）（从4开始八步，总产率43%）。该方法还用于制备立体特异性氘代CCG-III（d-18）和光学富集的（-）-18。22的去质子化导致环丙烷开环，得到苯并吲嗪（23）。
The addition of carbon and heteroatom nucleophiles to (bicyclo[5.1.0]octadienyl)Fe(CO)2L+cations5or8(L = CO, PPh3) generally proceeds via attack at the dienyl terminus on the face of the ligand opposite to iron to generate 6-substituted (bicyclo[5.1.0]octa-2,4-diene)iron complexes (11or13). In certain cases, these products are unstable with respect to elimination of a proton and the nucleophilic substituent to afford (cyclooctatetraene)Fe(CO)2L (4or7). Decomplexation of13f, arising from addition of phthalimide to8, gaveN-(bicyclo[5.1.0]octa-3,5-dien-2-yl)phthalimide (19). Oxidative cleavage of19(RuCl3/NaIO4) followed by esterification gave the cyclopropane diester22, which upon hydrolysis gavecis-2-(2‘-carboxycyclopropyl)glycine (CCG-III,18)(eight steps from4, 43% overall yield). This methodology was also utilized for preparation of stereospecifically deuterated CCG-III (d-18) and optically enriched (−)-18. Deprotonation of22resulted in cyclopropane ring opening to afford the benzoindolizidine (23).