ChemInform Abstract: Gibberellins. Part 118. Computer-Assisted Site-Specific Functionalization in the Gibberellin Series: Norrish Type II Photocyclization via a 9-Membered Transition State.

ChemInform ◽  
1988 ◽  
Vol 19 (15) ◽  
Author(s):  
G. ADAM ◽  
A. PREISS ◽  
PHAM DINH HUNG PHAM DINH HUNG ◽  
L. KUTSCHABSKY
1971 ◽  
Vol 49 (8) ◽  
pp. 1310-1314 ◽  
Author(s):  
L. P-Y. Lee ◽  
B. McAneney ◽  
J. E. Guillet

Studies of the photolysis of 4-methyl 3-hexanone and the iso-electronic 2-methoxy 3-pentanone have been made in hydrocarbon solution using light of wavelength 313 nm. The latter compound gives only Norrish type II products with a quantum yield of 0.19 ±.01. The former gives a predominance of type I products with a total quantum yield of 0.23 ±.01 and the quantum yield for type II is reduced to 0.10 ±.01. The predominant type I reaction appears to involve α-scission to give an ethyl and a 2-methyl butyryl radical, which suggests a "cage effect". It is suggested that the reason for the suppression of the type I reaction in 2-methoxy 3-pentanone is the greater ease of γ-hydrogen abstraction due to the presence of the oxygen atom in a six-membered transition state.


2020 ◽  
Author(s):  
Pierpaolo Morgante ◽  
Charitha Guruge ◽  
Yannick P. Ouedraogo ◽  
Nasri Nesnas ◽  
Roberto Peverati

The 7-nitroindolinyl family of caging chromophores has received a lot of attention in the past two decades. However, it is not clear if they undergo cyclization or migration upon photo-uncaging to release the active compound. In this study, we performed state-of-the-art density functional theory calculations to fully understand the photo-uncaging mechanism and we compared the probabilities of all plausible pathways. We found that the key transition state in the lowest¬ energy pathway involves an acyl migration. It possesses the characteristics of a combined Norrish Type I and a 1,6-nitro-acyl variation of a Norrish Type II mechanism, which has not been previously reported. We also introduced a new computational procedure that allows the estimation of intersystem crossing rate constants useful to compare the relative quantum yield of substituted cages. This procedure may pave the way for improved cage designs that possess higher quantum yields and more efficient agonist release.<br><br>


1976 ◽  
Vol 54 (20) ◽  
pp. 3117-3124 ◽  
Author(s):  
Yoshihisa Inoue ◽  
Setsuo Takamuku ◽  
Hiroshi Sakurai

Upon mercury photosensitization, the vibrationally excited triplet of the simple alkenes 1-hexene and cis-2-octene undergoes an olefinic type II reaction consisting of an intramolecular 1,5-hydrogen abstraction via a six-membered transition state and subsequent reaction of the resulting biradical, in sharp contrast to the well established allylic C—C and C—H bond cleavage of alkenes without a γ-hydrogen. The cis–trans photoisomerization of cis-2-octene and other intramolecular hydrogen abstractions of minor importance occurring through unfavorable transition states were also observed. The mercury photosensitization of various cyclic and acyclic alkenes so far reported are comparatively discussed.


2021 ◽  
Author(s):  
Timothy J Yee ◽  
Michael J Strong ◽  
Matthew S Willsey ◽  
Mark E Oppenlander

Abstract Nonunion of a type II odontoid fracture after the placement of an anterior odontoid screw can occur despite careful patient selection. Countervailing factors to successful fusion include the vascular watershed zone between the odontoid process and body of C2 as well as the relatively low surface area available for fusion. Patient-specific factors include osteoporosis, advanced age, and poor fracture fragment apposition. Cervical 1-2 posterior instrumented fusion is indicated for symptomatic nonunion. The technique leverages the larger posterolateral surface area for fusion and does not rely on bony growth in a watershed zone. Although loss of up to half of cervical rotation is expected after C1-2 arthrodesis, this may be better tolerated in the elderly, who may have lower physical demands than younger patients. In this video, we discuss the case of a 75-yr-old woman presenting with intractable mechanical cervicalgia 7 mo after sustaining a type II odontoid fracture and undergoing anterior odontoid screw placement at an outside institution. Cervical radiography and computed tomography exhibited haloing around the screw and nonunion across the fracture. We demonstrate C1-2 posterior instrumented fusion with Goel-Harms technique (C1 lateral mass and C2 pedicle screws), utilizing computer-assisted navigation, and modified Sonntag technique with rib strut autograft.  Posterior C1-2-instrumented fusion with rib strut autograft is an essential technique in the spine surgeon's armamentarium for the management of C1-2 instability, which can be a sequela of type II dens fracture. Detailed video demonstration has not been published to date.  Appropriate patient consent was obtained.


2014 ◽  
Vol 50 (94) ◽  
pp. 14724-14727 ◽  
Author(s):  
Ming Cheng ◽  
Wei Zhang ◽  
Jinghe Yuan ◽  
Wangxi Luo ◽  
Nan Li ◽  
...  

Single-molecule dynamics of the transforming growth factor type II receptor (TβRII) labeled by an unnatural amino acid.


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