A remarkably short (four steps, 31% overall yield) enantioselective synthesis of the structurally unique C2-symmetric tetracyclic triterpene (+)-alpha-onocerin (1) has been developed. The brevity of this mechanism depends on the assembly of four fragments (two molecules of a chiral epoxy ketone and two molecules of vinyllithium) to generate the chiral bis-epoxide 4 in one step, and on the efficient formation of all four carbocyclic rings in one step by cation-olefin tetracyclization. New and general methodology for the conversion of vinyl tert-butyldimethylsilyl ethers to vinyl triflates with retention of E or Z olefinic geometry also was utilized in the synthesis of 1. A short enantioselective synthesis of a non-C2-symmetric diastereomer of 1 is also described which uses the new methodology.
The total synthesis of Kopsia lapidilecta alkaloid (+/-)-lapidilectine B is described. Notable elements of this synthesis include the first natural products application of the Smalley azido-enolate cyclization to form the 1,2-dihydro-3H-indol-3-one (indoxyl) core and installation of the pyrrolidine ring by a 2-azaallyllithium [3+2] cycloaddition with the acetylene equivalent phenyl vinyl sulfide. Closure of the eight-membered perhydroazocine ring is accomplished via the intramolecular S(N)2 substitution of a mesylate. This constitutes the first synthesis of a member of the 5,6,12,13-tetrahydro-11a,13a-ethano-3H-pyrrolo[1',2':1,8]azocino[5,4-b]indole class of alkaloids.
The leakage flow is that liquid does not push gas bubbles and leaks through the channel corners. This leakage flow was confirmed by tracking particles moving in the liquid film with a double light path method and was quantified by tracking the gas-liquid interface movement. The results show that leakage flow varies during bubble formation process. The average net leakage flow Q net-leak in a bubble formation cycle at T-junction can be as large as 62.4% of the feeding liquid flow rate, depending on the liquid properties. Q net-leak for regular flow at main channel is much smaller, ranging from about 0 to 30% of the feeding liquid flow rate. The difference between the two leakage flows would lead to an increase in liquid slug length after generation. Finally, the effects of parameters such as phase flow rates, surface tension, and viscosity were investigated.
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