Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405, USA.
J Am Chem Soc. 2012 Dec 26;134(51):20569-72. doi: 10.1021/ja305467x. Epub 2012 Oct 31.
The theoretically inspired development of a Rh-catalyzed [3 + 2 + 1] carbocyclization of carbon- and heteroatom-tethered alkenylidenecyclopropanes (ACPs) with CO for the stereoselective construction of cis-fused bicyclohexenones is described. This study demonstrates that the ring opening of alkylidenecyclopropane proceeds through a Rh(III)-trimethylenemethane complex, which undergoes rate-determining carbometalation through a transition state that accurately predicts the stereochemical outcome for this process. The experimental studies demonstrate the validity of this approach and include the first highly enantioselective reaction involving an ACP to highlight further the synthetic utility of this transformation.
本文描述了受理论启发的 Rh 催化[3+2+1]碳环化反应，该反应涉及碳和杂原子键合的烯基烯丙基环丙烷（ACPs）与 CO 的反应，用于立体选择性构建顺式稠合双环环己烯酮。该研究表明，亚烷基环丙烷的开环通过 Rh(III)-三甲叉甲烷络合物进行，该络合物通过准确预测该过程立体化学结果的过渡态进行速率决定的碳金属化。实验研究证明了该方法的有效性，包括首例涉及 ACP 的高对映选择性反应，进一步突出了这种转化的合成实用性。
