401. Mechanism and origins of ligand-controlled Pd(II)-catalyzed regiodivergent carbonylation of alkynes.
- Author
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Liu, Jian-Biao, Zhang, Xin, Tian, Ying-Ying, Wang, Xin, Zhu, Xun-Kun, and Chen, De-Zhan
- Subjects
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CARBONYLATION , *NUCLEOPHILIC reactions , *DENSITY functional theory , *FUNCTIONAL groups , *POLAR effects (Chemistry) , *PROTON transfer reactions - Abstract
Transition-metal-catalyzed carbonylation provides a useful approach to synthesize carbonyl-containing compounds and their derivatives. Controlling the regio-, chemo-, and stereoselectivity remains a significant challenge and is the key to the success of transformation. In the present study, we explored the mechanism and origins of the ligand-controlled regiodivergent carbonylation of alkynes with competitive nucleophilic amino and hydroxy groups by density functional theory (DFT) calculations. The proposed mechanism involves O(N)-cyclization, CO insertion, N–H(O–H) cleavage, C–N(C–O) reductive elimination and regeneration of the catalyst. The chemoselectivity is determined by cyclization. Instead of the originally proposed switch of competitive coordination sites, a new type of concerted deprotonation/cyclization model was proposed to rationalize the ligand-tuned chemoselectivity. The electron-deficient nitrogen-containing ligand promotes the flow of electrons during cyclization, and so it favors the O-cyclization/N-carbonylation pathway. However, sterically bulky and electron-rich phosphine controls the selectivity by a combination of electronic and steric effects. The improved mechanistic understanding will enable further design of selective transition-metal-catalyzed carbonylation. [ABSTRACT FROM AUTHOR]
- Published
- 2019
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