Diastereoselective carbenes: Stereoelectronic control of bent singlet trans-2 '-substituted cyclobutylcarbenes

作者：Rosenberg Murray G; Brinker Udo H^*

来源：Tetrahedron Letters, 2018, 59(7): 645-649.

DOI：10.1016/j.tetlet.2018.01.006

• Carbenes
• Cyclobutanes
• Stereoselectivity
• Inductive effects
• Computational studies

The UM06-2X/aug-cc-pVTZ//UM06-2X/6-311G(d) theoretical models of representative singlet trans-2'-substituted cyclobutylcarbenes were computed. The :CH-group of carbenes with an ERG is bent toward the c-C4H7-ring's proximal C1'-C2' single bond. The :CH-group of carbenes with an EWG is bent toward the c-C4H7-ring's distal C1'-C4' single bond. The contrasting stereoelectronic effect was computationally tested using trimethylsilyl vs. bromo substituents to determine if exo-1- and exo-2-substituted bicyclo [2.1.0] pentanes would be produced in diastereomeric excess.

• 出版日期2018-2-14