A cycloaddition cascade approach to the total synthesis of (-)-FR182877

被引：109

作者：

Evans, DA ^{[1
]}

Starr, JT ^{[1
]}

机构：

[1] Harvard Univ, Dept Chem & Chem Biol, Cambridge, MA 02138 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2003年 / 125卷 / 44期

关键词：

D O I：

10.1021/ja037643+

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

An asymmetric synthesis of the cytotoxic natural product, (-)-FR182877 (1), has been achieved. Chirality for the entire structure was established using two (4R)-4-benzyl-2-oxazolidinone-mediated boron aldol reactions. A 19-membered macrocarbocycle was synthesized by the coupling of two fragments using a regioselective Suzuki coupling (17 + 23 --> 26; 84%) and macrocyclization of a beta-keto ester (30 - 31; 77%). Oxidation of 31 triggered a sequence of stereoselective transannular Diels-Alder reactions (32 --> 34; 63%) forming four new rings and seven new stereocenters in the pivotal construction event. This pentacyclic intermediate was subsequently transformed to (-)-FR182877. Semiempirical calculations of the transannular Diels-Alder cycloaddition cascade were carried out to determine the origins of asymmetric induction.

引用

页码：13531 / 13540

页数：10

共 49 条

[1] Asymmetric synthesis of the F-pyran fragment of the altohyrtins [J].

Anderson, JC ;

McDermott, BP .

TETRAHEDRON LETTERS, 1999, 40 (39) :7135-7138

[2] DIALKYLBORANE-CATALYZED HYDROBORATION OF ALKYNES WITH 1,3,2-BENZODIOXABOROLE IN TETRAHYDROFURAN [J].

ARASE, A ;

HOSHI, M ;

MIJIN, A ;

NISHI, K .

SYNTHETIC COMMUNICATIONS, 1995, 25 (13) :1957-1962

[3] A one-step synthesis of tetrahydropyranopyranones from carbonyl compounds [J].

Armstrong, A ;

Goldberg, FW ;

Sandham, DA .

TETRAHEDRON LETTERS, 2001, 42 (27) :4585-4587

[4]

COREY EJ, 1972, TETRAHEDRON LETT, P3769

[5] A USEFUL 12-I-5 TRIACETOXYPERIODINANE (THE DESS-MARTIN PERIODINANE) FOR THE SELECTIVE OXIDATION OF PRIMARY OR SECONDARY ALCOHOLS AND A VARIETY OF RELATED 12-I-5 SPECIES [J].

DESS, DB ;

MARTIN, JC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (19) :7277-7287

[6]

Evans DA, 2002, ANGEW CHEM INT EDIT, V41, P1787, DOI 10.1002/1521-3773(20020517)41:10<1787::AID-ANIE1787>3.0.CO

[7]

2-V

[8] Synthesis and absolute stereochemical assignment of (+)-miyakolide [J].

Evans, DA ;

Ripin, DHB ;

Halstead, DP ;

Campos, KR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (29) :6816-6826

[9] C-13 NMR CHEMICAL-SHIFT CORRELATIONS IN 1,3-DIOL ACETONIDES - IMPLICATIONS FOR THE STEREOCHEMICAL ASSIGNMENT OF PROPIONATE-DERIVED POLYOLS [J].

EVANS, DA ;

RIEGER, DL ;

GAGE, JR .

TETRAHEDRON LETTERS, 1990, 31 (49) :7099-7100

[10] Use of thallium(I) ethoxide in Suzuki cross coupling reactions [J].

Frank, SA ;

Chen, H ;

Kunz, RK ;

Schnaderbeck, MJ ;

Roush, WR .

ORGANIC LETTERS, 2000, 2 (17) :2691-2694

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