Nitroso-ene cyclization enabled access to 1-azaspiro[4.4]nonane and its application in a modular synthesis toward (±)-cephalotaxine

被引：24

作者：

Huang, Sha-Hua ^{[1
,2
]}

Tian, Xuechao ^{[1
]}

Mi, Xianwei ^{[2
]}

Wang, Yan ^{[2
]}

Hong, Ran ^{[2
]}

机构：

[1] Shanghai Inst Technol, Sch Chem & Environm Engn, Shanghai 201418, Peoples R China

[2] Chinese Acad Sci, Key Lab Synthet Chem Nat Subst, Shanghai Inst Organ Chem, Shanghai 200032, Peoples R China

来源：

TETRAHEDRON LETTERS | 2015年 / 56卷 / 48期

基金：

中国国家自然科学基金;

关键词：

Alkaloids; Azaspirocycle; Heck reaction; Modular synthesis; Nitroso-ene cyclization; ENANTIOSELECTIVE TOTAL-SYNTHESIS; FORMAL TOTAL-SYNTHESIS; POTENT IMMUNOSUPPRESSANT FR901483; EFFICIENT SYNTHESIS; ACYLNITROSO COMPOUNDS; VCAM-1; INDUCTION; NATURAL-PRODUCTS; PINNAIC ACID; HALICHLORINE; (-)-FR901483;

D O I：

10.1016/j.tetlet.2015.10.002

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

In this communication, a nitroso-ene cyclization was devised to rapidly construct 1-azaspiro[4.4]nonane, a key structural motif which was further implemented into the modular synthesis of (+/-)-cephalotaxine (6). The whole synthesis route to access the key intermediate 7 involves eight steps from a commercially available 1,2-epoxycyclopentane (12) and five purifications on silica gel column. The direct nitroso-ene reaction to 1-azabicyclo[4.4]non-2-one paves a way to a future development of the practical synthesis of cephalotaxus alkaloids. (C) 2015 Published by Elsevier Ltd.

引用

页码：6656 / 6658

页数：3

共 7 条

[1] Highly efficient asymmetric access to 1-azaspiro[4.4]nonane skeleton
Planas, L
Perard-Viret, J
Royer, J
Selkti, M
Thomas, A
SYNLETT, 2002, (10) : 1629 - 1632
[2] SYNTHESIS AND REACTIONS OF 1-AZASPIROCYCLES - 1-AZASPIRO[4.5]DECANE AND 1-AZASPIRO[4.4]NONANE RING-SYSTEMS
BRYCE, MR
GARDINER, JM
HORTON, PJ
SMITH, SA
JOURNAL OF CHEMICAL RESEARCH-S, 1989, (01): : 1 - 1
[3] Synthesis of 1-Azaspiro[4.4]nonane Derivatives Enabled by Domino Radical Bicyclization Involving Formation and Capture of Alkoxyaminyl Radicals
Guerrero-Caicedo, Alejandro
Soto-Martinez, Diana M.
Osorio, David A.
Novoa, Muskendol
Loaiza, Alix E.
Jaramillo-Gomez, Luz M.
ACS OMEGA, 2019, 4 (25): : 21100 - 21114
[4] Enantioselective synthesis of (R)-1-azaspiro[4.4]nonane-2,6-dione ethylene ketal, key chiral intermediate in the elaboration of (-)-cephalotaxine
Pizzonero, M
Dumas, F
d'Angelo, J
HETEROCYCLES, 2005, 66 : 31 - 37
[5] Total Synthesis of Immunosuppressive Mycestericin E and G Enabled by a Highly Stereoselective Nitroso-Ene Cyclization
Zhao, Yao
Ding, Yuzhen
Peng, Yalan
Wang, Yang
Han, Shiqing
Zhu, Lili
Huang, Sha-Hua
Hong, Ran
ORGANIC LETTERS, 2023, 25 (19) : 3497 - 3501
[6] 1-Azaspiro[4.4]nonane-2,6-dione and the separation and absolute configurations of its enantiomers
Nagasaka, T
Sato, H
Saeki, S
TETRAHEDRON-ASYMMETRY, 1997, 8 (02) : 191 - 194
[7] Metal free synthesis of 1-azaspiro[4.4]nonane-3-one system via reactions of nitrones with 1,1-disubstituted allenes
Amrutha, U.
Babu, Beneesh P.
Prathapan, Sreedharan
JOURNAL OF HETEROCYCLIC CHEMISTRY, 2019, 56 (12) : 3236 - 3243

← 1 →