Preparation of THP-Ester-Derived Pyridinium-Type Salts and their Reactions with Various Nucleophiles

被引：12

作者：

Fujioka, Hiromichi ^{[1
]}

Minamitsuji, Yutaka ^{[1
]}

Moriya, Takahiro ^{[1
]}

Okamoto, Kazuhisa ^{[1
]}

Kubo, Ozora ^{[1
]}

Matsushita, Tomoyo ^{[1
]}

Murai, Kenichi ^{[1
]}

机构：

[1] Osaka Univ, Grad Sch Pharmaceut Sci, Suita, Osaka 5650871, Japan

来源：

CHEMISTRY-AN ASIAN JOURNAL | 2012年 / 7卷 / 08期

关键词：

nucleophilic substitution; protecting groups; salt effect; synthetic methods; tetrahydropyran; ALPHA-SELECTIVE GLYCOSYLATIONS; EFFICIENT DEPROTECTION; BETA-MANNOPYRANOSIDES; COMBINATION; ACETALS; REAGENT; 2,6-DIDEOXYTHIOGLYCOSIDES; CYCLOADDITION; SPECULATION; ALKYLATION;

D O I：

10.1002/asia.201200234

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Nucleophilic substitution at the anomeric positions of tetrahydropyranyl (THP) and related carbohydrate-derived esters that proceeded through pyridinium-type salt intermediates have been developed. Treatment of the 6-substituted a-acetoxy-tetrahydropyrans with TMSOTf (TMS=trimethylsilyl) and 2-substitutited pyridines, such as 2-p-tolylpyridine and 2-methoxypyridine, led to the efficient generation of cis-pyridinium-type salts. These salts reacted with various nucleophiles, such as alcohols, azides, and organozinc reagents, to form nucleophilic-substitution products. A characteristic feature of these processes was that they took place under mild conditions, which did not affect acid-labile protecting groups. Furthermore, the reactions that employed azides and C-nucleophiles generated 2,6-trans products with high degrees of stereoselectivity.

引用

页码：1925 / 1933

页数：9

共 76 条

[21] Unexpected highly chemoselective deprotection of the acetals from aldehydes and not ketones: TESOTf-2,6-lutidine combination [J].

Fujioka, H ;

Sawama, Y ;

Murata, N ;

Okitsu, T ;

Kubo, O ;

Matsuda, S ;

Kita, Y .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (38) :11800-11801

[22] Organic chemistry using weakly electrophilic salts:: Efficient formation of O,O-mixed, O,S- and N,O-acetals [J].

Fujioka, Hiromichi ;

Okitsu, Takashi ;

Ohnaka, Takuya ;

Li, Ruichuan ;

Kubo, Ozora ;

Okamoto, Kazuhisa ;

Sawama, Yoshinari ;

Kita, Yasuyuki .

JOURNAL OF ORGANIC CHEMISTRY, 2007, 72 (21) :7898-7902

[23] Alkyl- and arylation of oxacyclic ethers with triethylsilyl triflate-2,4,6-collidine-Gilman reagent combination: Remarkable discrimination of two ether oxygens [J].

Fujioka, Hiromichi ;

Ohnaka, Takuya ;

Okitsu, Takashi ;

Kubo, Ozora ;

Okamoto, Kazuhisa ;

Sawama, Yoshinari ;

Kita, Yasuyuki .

HETEROCYCLES, 2007, 72 :529-540

[24] Reaction of tetrahydropyranyl ethers with triethylsilyl trifluoromethanesulfonate-2,4,6-collidine combination: Speculation on the intermediate, efficient deprotection, and application to efficient ring-closing metathesis as a tether [J].

Fujioka, Hiromichi ;

Okitsu, Takashi ;

Ohnaka, Takuya ;

Sawama, Yoshinari ;

Kubo, Ozora ;

Okamoto, Kazuhisa ;

Kita, Yasuyuki .

ADVANCED SYNTHESIS & CATALYSIS, 2007, 349 (4-5) :636-646

[25] Highly chemoselective alkylation of acetals using TESOTf-2,4,6-collidine-Gilman reagent combination [J].

Fujioka, Hiromichi ;

Okitsu, Takashi ;

Sawarna, Yoshinari ;

Ohnaka, Takuya ;

Kita, Yasuyuki .

SYNLETT, 2006, (18) :3077-3080

[26] The reaction of acetal-type protective groups in combination with TMSOTf and 2,2′-bipyridyl; mild and chemoselective deprotection and direct conversion to other protective groups [J].

Fujioka, Hiromichi ;

Minamitsuji, Yutaka ;

Kubo, Ozora ;

Senami, Kento ;

Maegawa, Tomohiro .

TETRAHEDRON, 2011, 67 (16) :2949-2960

[27] Mild Deprotection of Methylene Acetals in Combination with Trimethylsilyl Triflate-2,2′-Bipyridyl [J].

Fujioka, Hiromichi ;

Senami, Kento ;

Kubo, Ozora ;

Yahata, Kenzo ;

Minamitsuji, Yutaka ;

Maegawa, Tomohiro .

CHEMICAL & PHARMACEUTICAL BULLETIN, 2010, 58 (03) :426-428

[28] Novel Regiocontrolled Protection of 1,2- and 1,3-Diols via Mild Cleavage of Methylene Acetals [J].

Fujioka, Hiromichi ;

Senami, Kento ;

Kubo, Ozora ;

Yahata, Kenzo ;

Minamitsuji, Yutaka ;

Maegawa, Tomohiro .

ORGANIC LETTERS, 2009, 11 (22) :5138-5141

[29] Remarkable effect of 2,2′-bipyridyl: mild and highly chemoselective deprotection of methoxymethyl (MOM) ethers in combination with TMSOTf (TESOTf)-2,2′-bipyridyl [J].

Fujioka, Hiromichi ;

Kubo, Ozora ;

Senami, Kento ;

Minamitsuji, Yutaka ;

Maegawa, Tomohiro .

CHEMICAL COMMUNICATIONS, 2009, (29) :4429-4431

[30] MILD AND EFFICIENT DEPROTECTION OF ACETAL-TYPE PROTECTING GROUPS OF HYDROXYL FUNCTIONS BY TRIETHYLSILYL TRIFLATE-2,4,6-COLLIDINE COMBINATION [J].

Fujioka, Hiromichi ;

Kubo, Ozora ;

Okamoto, Kazuhisa ;

Senami, Kento ;

Okitsu, Takashi ;

Ohnaka, Takuya ;

Sawama, Yoshinari ;

Kita, Yasuyuki .

HETEROCYCLES, 2009, 77 (02) :1089-1103

← 1 2 3 4 5 6 7 8 →