谢如刚
1.生物功能体系的分子模拟;2.高选择性有机合成反应;3.甾体和活性天然产物。
个性化签名
- 姓名:谢如刚
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学术头衔:
博士生导师
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学科领域:
有机化学
- 研究兴趣:1.生物功能体系的分子模拟;2.高选择性有机合成反应;3.甾体和活性天然产物。
谢如刚, 教授、博士生导师。1961年毕业于四川大学有机化学专业并留校任教至今。现任四川大学生物有机化学研究所所长。国家自然科学基金委员会第六、九、十届化学科学部专家评审组成员,中国化学会第二十五届理事,成都市化学化工学会常务理事,成都市化学化工学会有机化学化工专委会主任,《有机化学》等编委,《化学研究与应用》常务编委。享受国务院特殊津贴。四川省首批学术技术带头人。
主要研究方向:1.生物功能体系的分子模拟;2.高选择性有机合成反应;3.甾体和活性天然产物。
主持、主研项目约20项。获奖:1978年全国科学大会重要成果二等奖,1986年和1995年四川省科技进步三等奖,1983年四川省科协系统先进工作者。在生物有机化学、高选择性有机合成、天然产物和功能材料等领域发表学术论文 180余篇,其中在 Proc. Natl. Acad. Sci. USA 、 Chem Commun 、 Synlett 、 Tetrahedron 系列、 J. Mol. Cat. A-Chemical、《高等学校化学学报》 等杂志发表SCI收录论文80余篇。4项成果获奖,合著合译专著4部。《有机化学》、《应用化学》、《化学研究与应用》,《合成化学》四杂志的编委或常务编委。中国化学会第25届理事。国家自然科学基金第6届学科评审组委员。曾任四川大学有机化学教研室主任,现任四川大学生物有机化学研究所所长。受邀为美国纽约科学院成员。受聘为中核纳米材料研究发展中心特聘研究员。
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10
谢如刚
Journal of Molecular Catalysis A: Chemical 242(2005)57-61,-0001,():
-1年11月30日
A series of new chiral squaric amino alcohols derived from (R)-(+)-camphor and squaric acid were synthesized, and applied to the enantioselective reduction of prochiral ketones with borane to give secondary alcohols with excellent enantiomeric excesses (up to 99%).
Camphor, Squaric acid, Borane, Ketone, Asymmetric reduction
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谢如刚
PNAS April 13, 2004 vol. 101 no.15 5417-5420,-0001,():
-1年11月30日
It is found that the addition of hexamethylphosphoramide to the solution of an alkyne, Et2Zn, and (S)-1,1 -bi-2-naphthol in methylene chloride allows the generation of an alkynylzinc at room temperature and shows highly enantioselective additions to aldehydes. The mild condition for the formation of the alkynylzinc reagent enables the use of functional alkynes in this asymmetric reaction with excellent enantioselectivity. It avoids the reflux of the toluene solutions of the alkynes and Et2Zn as previously reported.
asymmetric catalysis alkynylzinc additions propargylic alcohols
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谢如刚
Chem. Commun., 2004, 188-189,-0001,():
-1年11月30日
In the presence of a catalytic amount of a simple copper salt, the coupling of imidazole with arylboronic acids was performed in methanol to give corresponding N-arylimidazoles in almost quantitative yields; this coupling reaction could also be performed in aqueous solutions to give N-arylimidazoles in excellent yields.
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谢如刚
Tetrahedron: Asymmetry 14(2003)3651-3656,-0001,():
-1年11月30日
Novel homochiral molecular tweezers comprised of two chiral macrocyclic polyamine skeletons have been developed. These homochiral artificial receptors exhibit excellent chiral recognition ability toward the enantiomers of L-and D-amino acid derivatives (up to KL/KD=7.9, G0=−5.12 kJ mol−1) in CHCl3 at 25.0℃.
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谢如刚
Journal of Molecular Catalysis A: Chemical 202(2003)17-22,-0001,():
-1年11月30日
Chiral metallomicellar supramolecular systems composed of lipophilic l-histidinol have been investigated for their catalytic activities and enantioselectivities in the hydrolysis of N-protected -amino acid esters. Kinetic evidence suggests that the mechanism of the deacylation promoted by ligand 4a with a hydroxyl group and 2a lacking a hydroxyl group is different. The apparent pKa of Zn2+-4a is 6.8 in the micelllar aggregate. The highest enantioselectivity in hydrolysis of R(S)-C12-Leu-PNP (kS/kR=3.01) was obtained with 4a-Zn2+ as catalyst.
Enantioselective hydrolysis, α-Amino acid esters, Chiral metallomicelles, l-Histidinol, Synthesis
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谢如刚
Journal of Molecular Catalysis A: Chemical 187(2002)195-200,-0001,():
-1年11月30日
Four new long chain alkyl substituted 2,6-dioxo-1,4,7,10-tetraazacyclododecanes bearing an alcohol pendant has been synthesized. They coordinate with metal ion (Zn2+, Cu2+, Ni2+, Co2+) to yield 1:1 five-coordinate complexes. The catalytic properties of these complexes have been investigated for the hydrolysis of bis(p-nitrophenyl) phosphate (BNPP) in comicellar solution. The alcohol pendant has a profound effect on the catalytic properties of macrocyclic complexes, and the nature of transition metal ion, micellar microenvironment, hydrolysis temperature, hydrophobic interactions between the metallocatalyst and substrate are also important factors in the hydrolysis ofBNPP. Under the physiological conditions (pH=7.41, 35±0.1℃), the complexes exhibit higher catalytic activity (up to over 2-3 orders of magnitude) than metal ion or ligand alone in the hydrolysis of BNPP in comicellar solution with 2mM Brij 35.
Synthesis, Macrocyclic polyamine, Hydrolysis, Phosphodiester, Comicelle
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谢如刚, 李明, 田安民
Vol. 44 No. 6 SCIENCE IN CHINA (Series B) December 2001,-0001,():
-1年11月30日
The ab initio molecular orbital study on the mechanism of enantioselective reduction of 3,3-dimethyl butanone-2 with borane catalyzed by chiral oxazaborolidine is performed. As illustrated, this enantioselective reduction is exothermic and goes mainly through the formations of the catalyst-borane adduct, the catalyst-borane-3,3-dimethyl butanone-2 adduct, and the catalyst-alkoxyborane adduct with a B-O-B-N 4-member ring and through the decomposition of the catalyst-alkoxyborane adduct with the regeneration of the catalyst. During the hydride transfer in the catalyst-borane-3,3-dimethyl butanone-2 adduct to form the catalyst-alkoxyborane adduct, the hydride transfer and the formation of the B-O-B-N 4-member ring in the catalyst-alkoxyborane adduct happen simultaneously. The controlling step for the reduction is the transfer of hydride from the borane moiety to the carbonyl carbon of 3,3-dimethyl butanone-2. The transition state for the hydride transfer is a twisted chair structure and the reduction leads to R-chiral alcohols.
chiral oxazaborolidine,, 3,, 3-dimethyl butanone-2,, enantioselective reduction,, ab initio.,
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谢如刚
Tetrahedron: Asymmetry 12(2001)1907-1912,-0001,():
-1年11月30日
A series of chiral bifunctional squaric prolinol ligands, having N, S substituents at C(3) of the squaric ring were synthesized and applied to the asymmetric borane reduction of prochiral ketones via an in situ formed chiral boron heterocycle, affording secondary alcohols with high yields and excellent enantiomeric excesses (up to 99%). The crystal structure of 5a was obtained and the mechanism of the catalytic asymmetric reduction is also discussed.
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谢如刚
Chem. Commun., 2001, 1816-1817,-0001,():
-1年11月30日
Novel chiral imidazole cyclophane receptors were synthesized by highly selective N-alkylation of the imidazolyl 1Nposition of the bridged histidine diester 2 with the dibromide in the presence of NaH; these receptors exhibit good chiral recognition toward the enantiomers of L-and D-amino acid derivatives (up to KD/KL=3.52, DDG0=23.11 kJ mol21) in CHCl3 at 25.0℃.
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谢如刚
Tetrahedron Letters 42(2001)1107-1110,-0001,():
-1年11月30日
Two series of new chiral ligands, squaric acid aminoalcohols and C2-symmetric squaric acid diaminoalcohols have been synthesized. The chiral oxazaborolidines formed in situ from these ligands have been used in the enantioselective borane reduction of prochiral ketones and diketones to afford alcohol products with up to 99% enantiomeric excesses. The structures of the ligands have an obvious effect on the ee of the resulting alcohols.
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