Novel and highly regio- and stereoselective nickel-catalyzed homoallylation of benzaldehyde with 1,3-dienes
Novel and highly regio- and stereoselective nickel-catalyzed homoallylation of benzaldehyde with 1,3-dienes
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DOI：
10.1021/ja973847c
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发表时间：
1998-04-29
影响因子：
15
通讯作者：
Tamaru, Y
中科院分区：
文献类型：
--
作者：
Kimura, M;Ezoe, A;Tamaru, Y
有机镍配合物在其亲核反应性方面不同于其他第10族元素的有机金属配合物。1由于这一特性，已经开发出许多有效的镍催化或促进的CC键形成反应。其中，羰基化合物和烷基及烯丙基卤化物与π-烯丙基镍的烯丙基化已被证明是特别有用的，并已被广泛用于天然和非天然产物的合成。4，5然而，不幸的是，这种方法需要化学计量的镍。最近，已经开发了π-烯丙基镍与醛的催化加成的有用形式，其促进ω-二烯基醛环化成2-[（E）-1-丙烯基]环烷醇（eq 1）。6 2-烯丙基环烷醇可以通过使用化学计量的在复杂条件下产生的“Ni-H”络合物（等式1）来选择性地获得。在此，我们公开了Ni（acac）2（acac）乙酰丙酮合）与三乙基硼烷的组合很好地催化苯甲醛与1，3-二烯的均烯丙基化，以优异的产率和显著的区域选择性和立体选择性提供1-苯基-4-戊烯醇2（等式2）。例如，如在运行2中举例说明的，
Organonickel complexes are distinctive in their nucleophilic reactivity from organometal complexes of the other group 10 elements. 1 By virtue of this characteristic, many efficient nickelcatalyzed or-promoted CC bond formation reactions have been developed. 2, 3 Among these, allylation of carbonyls and alkyl and allyl halides with π-allylnickels has proved to be particularly useful and has been utilized widely for the synthesis of natural and unnatural products. 4, 5 Unfortunately, however, this methodology requires a stoichiometric amount of nickel. Recently, a useful version of catalytic addition of π-allylnickel to aldehyde has been developed, which promotes the cyclization of ω-dienyl aldehydes to 2-[(E)-1-propenyl] cycloalkanols (eq 1). 6 2-Allylcycloalkanols may be obtained selectively by employing a stoichiometric amount of “Ni-H” complexes generated under sophisticated conditions (eq 1). 7Here, we disclose that Ni (acac) 2 (acac) acetylacetonato) in combination with triethylborane nicely catalyzes the homoallylation of benzaldehyde with 1, 3-dienes to provide 1-phenyl-4-pentenols 2 in excellent yields and with pronounced regio-and stereoselectivities (eq 2). For example, as exemplified in run 2,