4489-84-3Relevant articles and documents
Straightforward conversion of alcohols into dibenzenesulfonimides
Giovanelli, Emerson,Doris, Eric,Rousseau, Bernard
, p. 8457 - 8458 (2006)
The reaction of various alcohols with N-fluorodibenzenesulfonimide and triphenylphosphine leads to the corresponding dibenzenesulfonylated amines in high yields.
Lewis Base Catalysis Enables the Activation of Alcohols by means of Chloroformates as Phosgene Substitutes
Zoller, Ben,Stach, Tanja,Huy, Peter H.
, p. 5637 - 5643 (2020/09/21)
Nucleophilic substitutions (SN) are typically promoted by acid chlorides as sacrificial reagents to improve the thermodynamic driving force and lower kinetic barriers. However, the cheapest acid chloride phosgene (COCl2) is a highly toxic gas. Against this background, phenyl chloroformate (PCF) was discovered as inherently safer phosgene substitute for the SN-type formation of C?Cl and C?Br bonds using alcohols. Thereby, application of the Lewis bases 1-formylpyrroldine (FPyr) and diethylcyclopropenone (DEC) as catalysts turned out to be pivotal to shift the chemoselectivity in favor of halo alkane generation. Primary, secondary and tertiary, benzylic, allylic and aliphatic alcohols are appropriate starting materials. A variety of functional groups are tolerated, which includes even acid labile moieties such as tert-butyl esters and acetals. Since the by-product phenol can be isolated, a recycling to PCF with inexpensive phosgene would be feasible on a technical scale. Eventually, a thorough competitive study demonstrated that PCF is indeed superior to phosgene and other substitutes.
A Relay Strategy Actuates Pre-Existing Trisubstituted Olefins in Monoterpenoids for Cross-Metathesis with Trisubstituted Alkenes
Bahou, Karim A.,Braddock, D. Christopher,Meyer, Adam G.,Savage, G. Paul,Shi, Zhensheng,He, Tianyou
, p. 4906 - 4917 (2020/04/10)
A retrosynthetic disconnection-reconnection analysis of epoxypolyenes - substrates that can undergo cyclization to podocarpane-type tricycles - reveals relay-actuated Δ6,7-functionalized monoterpenoid alcohols for ruthenium benzylidene catalyzed olefin cross-metathesis with homoprenyl benzenes. Successful implementation of this approach provided several epoxypolyenes as expected (E/Z, ca. 2-3:1). The method is further generalized for the cross-metathesis of pre-existing trisubstituted olefins in other relay-actuated Δ6,7-functionalized monoterpenoid alcohols with various other trisubstituted alkenes to form new trisubstituted olefins. Epoxypolyene cyclization of an enantiomerically pure, but geometrically impure, epoxypolyene substrate provides an enantiomerically pure, trans-fused, podocarpane-type tricycle (from the E-geometrical isomer).