Catalytic carbonylation reactions of benzyne derivatives
Catalytic carbonylation reactions of benzyne derivatives
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DOI：
10.1021/ja011923c
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发表时间：
2001-12-19
影响因子：
15
通讯作者：
Murai, S
中科院分区：
文献类型：
--
作者：
Chatani, N;Kamitani, A;Murai, S
在环加成反应中，炔烃可作为双碳组装单元，已有多种过渡金属催化的炔烃环加成反应的报道。1相反，苯并炔类化合物虽然能够进行环加成反应，但在过渡金属催化的环加成化学领域并没有得到广泛的应用。2苯乙炔的高反应性和短寿命表明，将其用作催化反应的组分可能很困难。在我们正在进行的催化碳化环加成反应的研究中，3我们研究了苯炔作为反应伙伴在碳化环加成反应中的应用。1999年，Pérez和Guitián报告说，2-三甲基硅基苯基三氟甲磺酸(1a)与CSF和催化量的Pd(0)在CH3CN中处理得到三苯，可能是通过苯的[2+2+2]同环三聚反应。4他们还报道了Pd催化的[2+2+2]苯并炔或苯并炔共环三聚反应制备菲或萘衍生物。5，6 Yamamoto独立报道了Pd(0)络合物催化的苯并炔-苯并炔-炔的类似的共环三聚反应。山本后来证实，这些共环三聚反应不是通过全自由苯并机理进行的；相反，催化循环的第一步涉及苯并前体1a中的Ar-OTf键与Pd(0)的氧化加成。8 Yamamoto还报道，在CSF的存在下，Pd催化的1a与烯丙基氯化物的反应生成了菲的衍生物，该反应通过游离苯并机理进行。8，9另一方面，到目前为止，还没有关于苯炔的催化羰化反应的报道。然而，苯并-过渡金属络合物与CO的化学计量反应是已知的。10如果苯炔能够以与炔烃相同的方式用作两碳组装单元，则一种新型的羰基化环加成反应是可能的。据我们所知，我们想要报道的是第一个过渡金属催化的苯的羰基化反应的例子。尽管人们考察了各种各样的反应体系，希望实现苯、各种烯烃(或炔烃)和CO的三组分环加成反应，但我们无法实现羰基环加成反应。然而，研究发现，少数配合物对苯炔本身的羰基化反应表现出催化活性。发现一种钴的络合物对苯乙炔的羰基化反应非常活跃。因此，1a(0.5 mm ol)与CO(5 Atm)在CH3CN(3 M L)中，在CO2(CO)8(0.01 m ol)和CSF(1 M Ol)的存在下，在60℃下反应12 h，以71%的产率得到了蒽醌(2a)11，同时还有微量的三苯(式1)。确实是
Alkynes can be used as two-carbon assembling units in cycloaddition reactions, and a variety of transition metal-catalyzed cycloaddition reactions using alkynes have been reported. 1 In contrast, benzyne derivatives (arynes) have not been used extensively in the area of transition metal-catalyzed cycloaddition chemistry despite their ability to undergo cycloaddition reactions. 2 The high reactivity and short lifetime of benzyne suggest that its use as a component of a catalytic reaction might be difficult. During our ongoing studies of catalytic carbonylative cycloaddition reactions, 3 we have investigated the use of benzyne as a reactive partner in carbonylative cycloadditions. In 1999, Pérez and Guitián reported that the treatment of 2-trimethylsilylphenyl trifluoromethansulfonate (1a) with CsF and a catalytic amount of Pd (0) in CH3CN gives triphenylene, possibly via the [2+ 2+ 2] homo-cyclotrimerization of benzyne. 4 They also reported on the preparation of phenanthrene or naphthalene derivatives via the Pd-catalyzed [2+ 2+ 2] co-cyclotrimerization of benzyne-benzyne-alkyne or benzyne-alkyne-alkyne. 5, 6 Yamamoto independently reported on a similar co-cyclotrimerization of benzyne-benzyne-alkyne, catalyzed by a Pd (0) complex. 7 Yamamoto later confirmed that these co-cyclotrimerization reactions do not proceed via an all-free benzyne mechanism; rather, the initial step of the catalytic cycle involves the oxidative addition of an Ar-OTf bond in benzyne precursor 1a to Pd (0). 8 Yamamoto also reported that the Pd-catalyzed reaction of 1a with allyl chlorides in the presence of CsF gives phenanthrene derivatives and that this reaction proceeded via a free benzyne mechanism. 8, 9 On the other hand, no report on the catalytic carbonylation of benzyne has appeared in the literature to date. Stoichiometric reactions of benzyne-transition metal complexes with CO are, however, known. 10 If benzyne could be utilized as a two-carbon assembly unit in the same manner as alkynes, a new type of carbonylative cycloaddition reaction is possible. We wish to report, to the best of our knowledge, the first example of transition metal-catalyzed carbonylation reactions of benzyne.Although a wide variety of reaction systems were examined in the hope of achieving the three-component cycloaddition of benzyne, various alkenes (or alkynes), and CO, we were not able to achieve the carbonylative cycloaddition reaction. However, it was found that a few complexes show catalytic activity for carbonylation reactions of benzyne itself. A cobalt complex was found to be extremely active for the carbonylation of benzyne. Thus, the reaction of 1a (0.5 mmol) with CO (5 atm) in CH3CN (3 mL) in the presence of Co2 (CO) 8 (0.01 mmol) and CsF (1 mmol) at 60 C for 12 h gave anthraquinone (2a) 11 in 71% isolated yield, along with a trace amount of triphenylene (eq 1). It was