Total synthesis of limonoids

TMS

1)SOCl2 O O
2)NaH/nBuLi

3)TBAF
OEt
OH

Cl

(E)-2,6-dimethyl-11-(trimethylsilyl)undeca-1,6-dien-10-yn-3-ol ethyl 2-chloro-3-oxobutanoate

Chemical Formula: C16H28OSi Chemical Formula: C6H9ClO3
Exact Mass: 264.19 Exact Mass: 164.02
Molecular Weight: 264.48 Molecular Weight: 164.59
m/z: 264.19 (100.0%), 265.19 (22.4%), 266.19 (4.2%), 266.20 (1.7%) m/z: 164.02 (100.0%), 166.02
Elemental Analysis: C, 72.66; H, 10.67; O, 6.05; Si, 10.62 (32.0%), 165.03 (6.7%), 167.02
(2.1%)
Elemental Analysis: C, 43.78; H,
5.51; Cl, 21.54; O, 29.16
• 
Name of reagents
  1- (SOCl2) Thionyl chloride
  2- (NaH/nBu4Li) Saline (Salt like hydride/n-butyllithium an organolithium reagent
  3-Tetra n-Butylammonium Fluoride(nBu4NF). It is a quaternary ammonium salt, a well-
known desilylating agent.
 •Catalysis
Thionyl chloride, SOCl2, is a reagent for converting alcohols to alkyl halides and
carboxylic acids to acid chlorides. n-Butyllithium is an organolithium reagent. TBAF is
used to remove silyl ether protecting groups. It is used as a phase transfer catalyst and
as a mild base.

•Reaction name with a brief introduction

Displacement reaction occurs. In this type of reaction, thionyl chloride is used for the
chlorination of alcohol. Allylic chloride is produced which could displace dianion beta keto
ester.
•Brief explanation of reaction step 
Sequential alcohol chlorination, alkene region selective epoxidation, propargylation, and
Ti(iii) mediated epoxide opening reaction generated allylic alcohol named as (E)-2,6-
dimethyl-11-(trimethylsilyl) undeca-1,6-diene-10-yn-3-ol. Exposure of (E)-2,6-dimethyl-11-
(trimethylsilyl) undeca-1,6-diene-10-yn-3-ol SOCl2 results in formation of ethyl 2-chloro-3-
oxobutanoate.
•Name of the Product

Ethyl 2-chloro-3-oxobutanoate