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41.
Simpson GL Heffron TP Merino E Jamison TF 《Journal of the American Chemical Society》2006,128(4):1056-1057
The combination of a trimethylsilyl group, a Br?nsted base, a fluoride source, and a hydroxylic solvent enables the first construction of the tetrad of tetrahydropyran rings found in the majority of the ladder polyether natural products by way of a cascade of epoxide-opening events that emulates the final step of Nakanishi's proposed biosynthetic pathway. The trimethylsilyl group disappears during the course of the cascade, and thus these are the first epoxide ring-opening cascades that afford ladder polyether subunits containing no directing groups at the end of the cascade. 相似文献
42.
Let {Xk} be a sequence of i.i.d. random variables with d.f. F(x). In the first part of the paper the weak convergence of the d.f.'s
Fn(x) of sums
is studied, where 0<α≤2, ank>0, 1≤k≤mn, and, as n→∞, bothmax
1≤k≤mna
nk→0 and
. It is shown that such convergence, with suitably chosen An's and necessarily stable limit laws, holds for all such arrays {αnk} provided it holds for the special case αnk=1/n, 1≤k≤n. Necessary and sufficient conditions for such convergence are classical. Conditions are given for the convergence
of the moments of the sequence {Fn(x)}, as well as for its convergence in mean. The second part of the paper deals with the almost sure convergence of sums
, where an≠0, bn>0, andmax
1≤k≤n ak/bn→0. The strong law is said to hold if there are constants An for which Sn→0 almost surely. Let N(0)=0 and N(x) equal the number of n≥1 for which bn/|an|<x if x>0. The main result is as follows. If the strong law holds,EN (|X1|)<∞. If
for some 0<p≤2, then the strong law holds with
if 1≤p≤2 and An=0 if 0<p<1. This extends the results of Heyde and of Jamison, Orey, and Pruitt. The strong law is shown to hold under various
conditions imposed on F(x), the coefficients an and bn, and the function N(x).
Proceedings of the Seminar on Stability Problems for Stochastic Models, Moscow, 1993. 相似文献
43.
Christopher P. Breen Prof. Dr. Timothy F. Jamison 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(64):14527-14531
A strategy for the continuous flow synthesis of angiotensin converting enzyme (ACE) inhibitors is described. An optimization effort guided by in situ IR analysis resulted in a general amide coupling approach facilitated by N-carboxyanhydride (NCA) activation that was further characterized by reaction kinetics analysis in batch. The three-step continuous process was demonstrated by synthesizing 8 different ACE inhibitors in up to 88 % yield with throughputs in the range of ≈0.5 g h−1, all while avoiding both isolation of reactive intermediates and process intensive reaction conditions. The process was further developed by preparing enalapril, a World Health Organization (WHO) essential medicine, in an industrially relevant flow platform that scaled throughput to ≈1 g h−1. 相似文献
44.
45.
Hyowon Seo Anne-Catherine Bédard Willie P. Chen Robert W. Hicklin Alexander Alabugin Timothy F. Jamison 《Tetrahedron》2018,74(25):3124-3128
Selective N-monomethylation of anilines has been achieved under continuous flow conditions using dimethyl carbonate as a green methylating agent in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene. Our methodology takes advantage of the expanded process windows available in the continuous flow regime to safely induce monomethylation in superheated solvents at high pressure. We propose selective N-monomethylation is achieved via an in situ protection-deprotection pathway, which is supported by the observed reactivities of several putative reaction intermediates. The robust and scalable method was applicable to a broad range of primary aniline substrates including ortho-, meta-, and para-substituted anilines, as well as electron-rich and electron-deficient anilines. The synthetic precursor of diazepam, 5-chloro-2-(methylamino)benzophenone, was selectively synthesized under our optimized conditions. 相似文献
46.
[reaction: see text] Highly regioselective, catalytic asymmetric reductive coupling reactions of 1,3-enynes and ketones have been achieved using catalytic amounts of Ni(cod)(2) and a P-chiral, monodentate ferrocenyl phosphine ligand. These couplings represent the first examples of catalytic, intermolecular reductive coupling of alkynes and ketones, enantioselective or otherwise, and afford synthetically useful 1,3-dienes possessing a quaternary carbinol stereogenic center in up to 70% ee. 相似文献
47.
[reaction: see text] A dicobalt hexacarbonyl (Co(2)(CO)(6)) cluster is essential for the unusually broad dipolarophile scope and for the sense and degree of diastereoselection in a catalytic, three-component synthesis of tetrahydrofurans and dihydrofurans. Likely involving a new class of carbonyl ylide, these cycloadditions are stereospecific with respect to the dipolarophile and exhibit high diastereoselectivity and regioselectivity in most cases. Differentiation of all four positions of the tetrahydrofuran can thus be accomplished in a triply convergent manner. 相似文献
48.
Eight P-chiral monodentate ferrocenyl phosphines (1a-h) were prepared in high enantiomeric excess (>95% ee in most cases) by way of an ephedrine-based oxazaphospholidine borane complex. Primary alkyl, secondary alkyl, and substituted aromatic substituents were successfully introduced at the phosphorus center, along with ferrocenyl and phenyl groups, generating phosphines of the general structure FcP(Ph)(R) (Fc = ferrocenyl, R = aryl, alkyl). The synthetic route employed provides facile access to a previously undeveloped class of chiral monophosphines. These compounds were evaluated as ligands in asymmetric catalytic reductive coupling of alkynes and aldehydes and were found to provide the desired chiral allylic alcohols with good regioselectivity and ee in many cases and with complete (E)-selectivity (>98:2) in all cases. 相似文献
49.
通过理论分析指出啁啾脉冲光谱仪探测法探测THz辐射存在时间分辨率极限,实验也得到了与理论分析相一致的结果.提出使用啁啾脉冲互相关法探测THz辐射,给予了一定的理论分析,实验结果证明此方法探测THz辐射的时间分辨率与传统的时间扫描延迟方法的时间分辨率相当.
关键词:
啁啾脉冲
THz辐射
互相关 相似文献
50.