Experimental and Theoretical Study of the 2-Alkoxyethylidene Rearrangement

详细信息    查看全文

• 作者：Kimberly S. Graves ; Dasan M. Thamattoor ; Paul R. Rablen
• 刊名：Journal of Organic Chemistry
• 出版年：2011
• 出版时间：March 18, 2011
• 年：2011
• 卷：76
• 期：6
• 页码：1584-1591
• 全文大小：948K
• 年卷期：v.76,no.6(March 18, 2011)
• ISSN：1520-6904

文摘

The rearrangement of 2-ethoxyethylidene, generated photochemically from a nonnitrogenous precursor, leads to ethyl vinyl ether. Although this product could result, in principle, from a 1,2-hydrogen shift and/or a 1,2-ethoxy shift in the carbene, a deuterium labeling study indicates an essentially exclusive preference for hydrogen migration. The experimental results are in agreement with CCSD and W1BD calculations for the simpler 2-methoxyethylidene system that show a prohibitively large barrier for the methoxy shift and a negligible barrier for the hydride shift.