Tertiary Alkylative Suzuki-Miyaura couplings

Synthesis ◽  
2022 ◽  
Author(s):  
Takashi Nishikata ◽  
Tom Sheppard ◽  
Naoki Tsuchiya

The Suzuki-Miyaura coupling is extremely useful to construct Csp2-Csp2 carbon bonds. On the other hand, Csp2-Csp3 coupling reactions are do not work well, and tert-alkylative Suzuki-Miyaura coupling is particularly challenging due to problematic oxidative addition and beta-hydride elimination side reactions. In this short review, we will introduce recent examples of tert-alkylative Suzuki-Miyaura couplings with tert-alkyl electrophiles or -boron reagents. The review will mainly focus on catalyst and product structures and the proposed mechanisms .

Synlett ◽  
2020 ◽  
Vol 31 (13) ◽  
pp. 1308-1312
Author(s):  
Tuan Thanh Dang ◽  
Peter Langer ◽  
Nguyen Thi Son ◽  
Tuan Anh Nguyen Tien ◽  
Marian Blanco Ponce ◽  
...  

Two-step sequential procedures for the Pd-catalyzed synthesis of 5- and 6-azaindoles are reported. The reactions proceed in very good yields. 6-Azaindoles are formed through site-selective Pd-catalyzed Sonogashira reaction of 3,4-dibromopyridine with alkynes, followed by a Pd-catalyzed tandem C–N coupling and cyclization with amines. On the other hand, 5-azaindoles are obtained by a site-selective Pd-catalyzed C–N coupling reaction of 3,4-dibromopyridine with amines, followed by C–C coupling and cyclization with alkynes.


2016 ◽  
Vol 01 (01) ◽  
pp. 27 ◽  
Author(s):  
Cuneyt Tetikkurt ◽  

Endobronchial involvement is a common feature of sarcoidosis. The mucosa may appear normal or there may be inflammatory changes with erythematous lesions, miliary nodules, and, rarely, mass-like lesions leading to obstruction. In patients with bronchial lesions, the bronchial biopsy may be positive in three-quarters of patients. On the other hand, granulomas may be identified in one-third of patients with a normal mucosa. Current data on endobronchial sarcoidosis is primarily associated with the treatment and prognosis of obstructive mass-like granulomas. Data relevant to clinical features of superficial endobronchial involvement and its implications on prognosis and extrapulmonary organ involvement is lacking. The results of our two previous studies reveal that clinical findings of endobronchial disease may be different. These studies also suggest that there is a great difference between patients with no endobronchial involvement, limited and diffuse endobronchial disease in regard to clinical features, and prognosis. The incidence of extrapulmonary organ involvement is also significantly different between the three groups. In this short review, the clinical findings of endobronchial sarcoidosis have been defined, the effects of superficial endobronchial involvement on prognosis, and extrapulmonary organ involvement.


2012 ◽  
Vol 07 ◽  
pp. 165-173 ◽  
Author(s):  
CHAO-JUN FENG ◽  
XIN-ZHOU LI

In this paper, we will give a short review on quantum spring, which is a Casimir effect from the helix boundary condition that proposed in our earlier works. The Casimir force parallel to the axis of the helix behaves very much like the force on a spring that obeys the Hooke's law when the ratio r of the pitch to the circumference of the helix is small, but in this case, the force comes from a quantum effect, so we would like to call it quantum spring. On the other hand, the force perpendicular to the axis decreases monotonously with the increasing of the ratio r. Both forces are attractive and their behaviors are the same in two and three dimensions.


1994 ◽  
Vol 67 (2) ◽  
pp. 299-313 ◽  
Author(s):  
Robert W. Layer ◽  
Dwight W. Chasar

Abstract Sulfenamide accelerators and sulfur donors based on secondary amines must liberate all of their amine in order to function. Consequently, they are capable of producing relatively large amounts of nitrosamines. Thiuram disulfides and dithiocarbamates, on the other hand, only liberate their amines because of undesired side reactions. Accordingly, compared to sulfenamides, they produce significant, but much lower levels of nitrosamines during the cure. In an effort to reduce these side reactions, and thus the amount of nitrosamine which forms, we investigated the effect of steric factors on nitrosamine formation. We find that thiurams and dithiocarbamates made from sterically bulky amines, like diisobutylamine, produce orders of magnitude lower levels of nitrosamine than TMTD. At the same time, when used as a kicker for 2-benzothiazole sulfenamides, N,N,N′,N′-tetraisobutylthiuram disulfide has better scorch safety but cures at the same rate as TMTD. Uniquely, N,N,N′,N′-tetraisobutylthiuram monosulfide acts as a retarder as well as a kicker for 2-benzothiazole sulfenamides.


1980 ◽  
Vol 45 (10) ◽  
pp. 2847-2854 ◽  
Author(s):  
Peter Gemeiner ◽  
Ľudovít Kuniak ◽  
Jiří Zemek

The O-alkylation of non cross-linked celluloses with p-nitrobenzyl chloride according to Campbell does not afford satisfying results (alkylation degree Da ⪬ 0.025). On the other hand, the use of cross-linked celluloses makes it possible to prepare p-nitrobenzyl cellulose under substantially milder reaction conditions (Da ⪬ 0.42); the degree of cross linking of cellulose considerably affected the Da of p-nitrobenzyl cellulose. The same also holds for O-alkylation of cross-linked celluloses with p-nitrobenzyl chloride according to Hakomori. Reduction of p-nitrobenzyl cellulose with dithionite is considerably associated with side reactions in which sulfur became embodied, whereas reduction with titanous chloride resulted in noticeable losses of p-nitrobenzyl groups. p-Aminobenzyl cellulose is, after activation with carboxyl groups, a suitable carrier for immobilization of enzymes as acetylcholinesterase, glucoamylase and α-amylase. The respective immobilized enzymes retained relatively high relative activities, in the last two cases also for high-molecular substrates.


1999 ◽  
Vol 173 ◽  
pp. 249-254
Author(s):  
A.M. Silva ◽  
R.D. Miró

AbstractWe have developed a model for theH2OandOHevolution in a comet outburst, assuming that together with the gas, a distribution of icy grains is ejected. With an initial mass of icy grains of 108kg released, theH2OandOHproductions are increased up to a factor two, and the growth curves change drastically in the first two days. The model is applied to eruptions detected in theOHradio monitorings and fits well with the slow variations in the flux. On the other hand, several events of short duration appear, consisting of a sudden rise ofOHflux, followed by a sudden decay on the second day. These apparent short bursts are frequently found as precursors of a more durable eruption. We suggest that both of them are part of a unique eruption, and that the sudden decay is due to collisions that de-excite theOHmaser, when it reaches the Cometopause region located at 1.35 × 105kmfrom the nucleus.


Author(s):  
A. V. Crewe

We have become accustomed to differentiating between the scanning microscope and the conventional transmission microscope according to the resolving power which the two instruments offer. The conventional microscope is capable of a point resolution of a few angstroms and line resolutions of periodic objects of about 1Å. On the other hand, the scanning microscope, in its normal form, is not ordinarily capable of a point resolution better than 100Å. Upon examining reasons for the 100Å limitation, it becomes clear that this is based more on tradition than reason, and in particular, it is a condition imposed upon the microscope by adherence to thermal sources of electrons.


Author(s):  
K.H. Westmacott

Life beyond 1MeV – like life after 40 – is not too different unless one takes advantage of past experience and is receptive to new opportunities. At first glance, the returns on performing electron microscopy at voltages greater than 1MeV diminish rather rapidly as the curves which describe the well-known advantages of HVEM often tend towards saturation. However, in a country with a significant HVEM capability, a good case can be made for investing in instruments with a range of maximum accelerating voltages. In this regard, the 1.5MeV KRATOS HVEM being installed in Berkeley will complement the other 650KeV, 1MeV, and 1.2MeV instruments currently operating in the U.S. One other consideration suggests that 1.5MeV is an optimum voltage machine – Its additional advantages may be purchased for not much more than a 1MeV instrument. On the other hand, the 3MeV HVEM's which seem to be operated at 2MeV maximum, are much more expensive.


2005 ◽  
Vol 19 (3) ◽  
pp. 129-132 ◽  
Author(s):  
Reimer Kornmann

Summary: My comment is basically restricted to the situation in which less-able students find themselves and refers only to literature in German. From this point of view I am basically able to confirm Marsh's results. It must, however, be said that with less-able pupils the opposite effect can be found: Levels of self-esteem in these pupils are raised, at least temporarily, by separate instruction, academic performance however drops; combined instruction, on the other hand, leads to improved academic performance, while levels of self-esteem drop. Apparently, the positive self-image of less-able pupils who receive separate instruction does not bring about the potential enhancement of academic performance one might expect from high-ability pupils receiving separate instruction. To resolve the dilemma, it is proposed that individual progress in learning be accentuated, and that comparisons with others be dispensed with. This fosters a self-image that can in equal measure be realistic and optimistic.


Author(s):  
Stefan Krause ◽  
Markus Appel

Abstract. Two experiments examined the influence of stories on recipients’ self-perceptions. Extending prior theory and research, our focus was on assimilation effects (i.e., changes in self-perception in line with a protagonist’s traits) as well as on contrast effects (i.e., changes in self-perception in contrast to a protagonist’s traits). In Experiment 1 ( N = 113), implicit and explicit conscientiousness were assessed after participants read a story about either a diligent or a negligent student. Moderation analyses showed that highly transported participants and participants with lower counterarguing scores assimilate the depicted traits of a story protagonist, as indicated by explicit, self-reported conscientiousness ratings. Participants, who were more critical toward a story (i.e., higher counterarguing) and with a lower degree of transportation, showed contrast effects. In Experiment 2 ( N = 103), we manipulated transportation and counterarguing, but we could not identify an effect on participants’ self-ascribed level of conscientiousness. A mini meta-analysis across both experiments revealed significant positive overall associations between transportation and counterarguing on the one hand and story-consistent self-reported conscientiousness on the other hand.


Sign in / Sign up

Export Citation Format

Share Document