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4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium
chloride was isolated and fully characterized.90,93 It is a stable
compound that can be stored in the solid state at room
temperature for up to a month or for several months in the
refrigerator, without detectable decomposition. This reagent
combined with carboxylic acid gave an active ester 21
(Scheme 19), and was used as condensing reagent for synthesis
of esters and amides.94¨C96
Taddei97 reported the application of DMTMM to the solidphase
synthesis of peptides. The yields and purity of the
products were high.Recently, Kaminski et al.98 introduced 4-(4,6-dimethoxy-
1,3,5-triazin-2-yl)-4-methylmorpholinium tetrafluoroborate
as a more stable reagent than the corresponding DMTMM
chloride. The new coupling reagent was used in ester and
peptide synthesis, in solution, and in solid-phase synthesis.
DMTMM 21 (Scheme 20) can be generated by different protocols
mentioned above. This active ester, without isolation
was used for many transformation of carboxylic group.
Giacomelli et al.99 prepared it using CDMTand applied it to
the synthesis of N-methoxy-N-methylamides, commonly
named Weinreb amides 22 (Scheme 20), a useful precursor
to ketones.100 A variety of these compounds were obtained
quantitatively from carboxylic acids, and N-protected amino
acids with high yields and purity.DMTMMwas also used for
this purpose, but the yields of Weinreb amides were lower.
It was reported that active ester 21 (Scheme 20), prepared
from DMTMM was reduced by hydrogen and Pt/C as the
catalyst to the corresponding aldehyde 23 (Scheme 20)
in good yields.101 Required optimization of the solvent,
hydrogen pressure, temperature, and time of reduction are
disadvantages to this method. Higher hydrogen pressure
(5 atm) gave alcohols.
Activated esters of aromatic carboxylic acid, and N-Boc or
N-Z protected a-amino acids were converted to ketones 25
(Scheme 20) or a-amino ketones by Grignard reagent in
the presence of stoichiometric amounts of CuI.102
Bandar and Pandit103 reported the synthesis of 2-oxazolines
26 (Scheme 20) from acyloxy triazine. The active ester was
reacted at room temperature with 2-amino-2-methyl-1-propanol
giving the desired product with good yields.
The same conditions, were used for the selective preparation
of monoacylated piperazine derivatives 27 (Scheme 20) with
good yields.104 Monoacylation of symmetrical diamines
often becomes problematic due to competitive bisacylation.

Recently, active ester 21 of formic acid was used for the
formylation of amines and a-amino acid esters 28 (Scheme
20). The reaction was conducted under reflux in methylene
chloride, or under microwave irradiation to reduce the
reaction time from hours to a few minutes. The yields
were high, the products pure and no significant racemization
of the chiral centers was observed.
Based on the reactivity of CC, Kunishima et al.106 published
preliminary data about a new immobilized dehydrocondensing
reagent in a polymerized form (Fig. 7). This polymer
reacts with carboxylic acids, in the presence of a NMM
like CDMT or DMTMM, giving active esters, which with
amines, gave amides in good yields.
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qq8489(½ð±Ò+50, ·­ÒëEPI+1): 2011-04-20 22:53:23
ringzhu(·­ÒëEPI-1): »úÆ÷·­Òë ÊÕ»ØEPI 2011-04-21 20:18:38
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