Probing the Formation of Bicyclo[4.2.0]octan-1-ols

Reaction of lithium enolates of simple ketones with (±)-phenyl vinyl sulfoxide has potential for the
convergent construction of complex fused ring systems containing a bicyclo[n.2.0]alkan-1-ol. The
formation of sulfinylbicyclo[4.2.0]octan-1-ols 1−3 from the lithium enolate of cyclohexanone with
(±)-phenyl vinyl sulfoxide or (R)-(+)-p-tolyl vinyl sulfoxide 18 was used to probe the mode of this
novel cyclization reaction. Using phenyl vinyl sulfoxide, variations in the reaction lighting and
solvent were investigated, in conjunction with radical trapping (TEMPO) and isotope labeling
(deuterium) experiments. Cyclization to form sulfinylbicyclooctanols 1−3 is likely to proceed via
an intermediate that ring closes to the bicycloalkanol anion 11 and was presently favored by the
use of solvents such as THF or DME.

简单酮的烯醇锂盐与(±)-苯基乙烯基亚砜的反应，在汇聚式构建含双环[n.2.0]烷-1-醇结构的复杂稠环体系方面具备应用潜力。本研究以环己酮的烯醇锂盐分别与(±)-苯基乙烯基亚砜、(R)-(+)-对甲苯基乙烯基亚砜18反应，生成亚磺酰基双环[4.2.0]辛烷-1-醇1~3，以此探究该新型环化反应的反应模式。在采用苯基乙烯基亚砜的反应体系中，我们考察了光照条件与溶剂对反应的影响，并结合自由基捕获（TEMPO）实验与氘同位素标记实验开展机制分析。生成亚磺酰基双环辛醇1~3的环化过程，大概率经由先环合得到双环烷醇负离子11的中间体路径进行，且在四氢呋喃（THF）、二甲氧基乙烷（DME）等溶剂中该反应路径更具优势。