Convenient Synthesis of 1-(Trimethylsilyl)- and 1-(Trimethylstannyl)Vinylphosphonates and Their Synthetic Application

Article abstract of DOI:10.1080/10426507.2014.978327

Dimethyl 1,1-bis(trimethylsilyl)methylphosphonate was succeeded to react with aromatic aldehydes in the presence of methyl benzoate as additive to give the corresponding vinylphosphonates in moderate yields. Michael addition and subsequent Peterson olefination reaction of dimethyl (Z)-2-(3,4-methylenedioxyphenyl)-1-(trimethylsilyl)vinylphosphonate with 3,4,5-trimethoxyphenyllithium and crotonaldehyde afforded the corresponding (2E,4E)-1-(3,4,5-trimethoxyphenyl)-1-(3,4-methylenedioxyphenyl)-2-(dimethylphosphono)hexa-2,4-diene in 36% yield.

Full text of DOI:10.1080/10426507.2014.978327

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Phosphorus, Sulfur, and Silicon and the
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Convenient Synthesis of
1-(Trimethylsilyl)- and 1-
(Trimethylstannyl)Vinylphosphonates and
Their Synthetic Application
Yoshiharu Okadaa, Riho Urushiharaa & Masato Nakamotoa
a Department of Biotechnology and Chemistry, Faculty of
Engineering, Kinki University, TakayaHigashi-Hiroshima, Japan
Accepted author version posted online: 06 Dec 2014.
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To cite this article: Yoshiharu Okada, Riho Urushihara & Masato Nakamoto (2015) Convenient
Synthesis of 1-(Trimethylsilyl)- and 1-(Trimethylstannyl)Vinylphosphonates and Their Synthetic
Application, Phosphorus, Sulfur, and Silicon and the Related Elements, 190:5-6, 922-924, DOI:
10.1080/10426507.2014.978327
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Phosphorus, Sulfur, and Silicon, 190:922–924, 2015
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2014.978327
CONVENIENT SYNTHESIS OF 1-(TRIMETHYLSILYL)-
AND 1-(TRIMETHYLSTANNYL)VINYLPHOSPHONATES
AND THEIR SYNTHETIC APPLICATION
Yoshiharu Okada, Riho Urushihara, and Masato Nakamoto
Department of Biotechnology and Chemistry, Faculty of Engineering, Kinki
University, Takaya, Higashi-Hiroshima, Japan
GRAPHICAL ABSTRACT
Abstract Dimethyl 1,1-bis(trimethylsilyl)methylphosphonate was succeeded to react with
aromatic aldehydes in the presence of methyl benzoate as additive to give the corresponding
vinylphosphonates in moderate yields. Michael addition and subsequent Peterson olefination
reaction of dimethyl (Z)-2-(3,4-methylenedioxyphenyl)-1-(trimethylsilyl)vinylphosphonate
with 3,4,5-trimethoxyphenyllithium and crotonaldehyde afforded the corresponding (2E,4E)-
1-(3,4,5-trimethoxyphenyl)-1-(3,4-methylenedioxyphenyl)-2-(dimethylphosphono)hexa-2,4-
diene in 36% yield.
Keywords Vinylphosphonates; vinylsilanes; vinylstannanes; Peterson reaction
Organophosphorus, organosilicon, and organotin compounds are useful intermediates
for organic synthesis. We became interested in the reactivity of multifunctionalized
methylphosphonates with carbonyl compounds. We report here a convenient synthesis of
vinylphosphonates with trimethylsilyl and trimethylstannyl groups in α-position from the
multifunctionalized methylphosphonates with trimethylsilyl and trimethylstannyl groups
1a,b (Figure 1).
Furthermore, the obtained vinylphosphonates were useful tandem reaction reagents,
e.g., in Michael reaction—Horner–Wadsworth–Emmons reaction. The reactions of 1a,b
Received 29 August 2014; accepted 15 October 2014.
Address correspondence to Yoshiharu Okada, Department of Biotechnology and Chemistry,
Faculty of Engineering, Kinki University, Umenobe 1, Takaya, Higashi-Hiroshima 739-2116, Japan. E-mail:
okadasan@hiro.kindai.ac.jp
922

923

924
Y. OKADA ET AL.
Figure 1 Functionalized dimethyl methylphosphonates.
with carbonyl compounds 2a–d in the presence of LDA in THF were carried out to give
Peterson reaction products 3a–d and 4a–d 1. The results are summarized in Table 1.
The reaction of 1a with benzaldehyde 2a did not give the desired product 3a; only
1a was recovered (entry 1). A similar reaction in the presence of methyl benzoate as an
additive gave a mixture of (E)-3a and (Z)-3a in 28% and 51% yields, respectively (entry
2). Also, sodium fluoride as an additive was effective (entry 3). The structures of (E)-3a–d,
1
(Z)-3a–d, (E)-4a–d, and (Z)-4a–d were assigned on the basis of their H and 13C NMR
spectra. The 1H NMR spectrum of (E)-3b shows a signal for olefinic proton at δ 8.22 (d, J =
35.2 Hz), while that of (Z)-3b shows the corresponding signal at δ 7.43 (d, J = 60.8 Hz).
Next, usage of a second functional group was investigated. Michael addition and
subsequent Peterson reaction of (Z)-3b with 3,4,5-trimethoxyphenyllithium and croton-
aldehyde afforded the desired (2E,4E)-5 in 37% yield (Eq. (1)).
REFERENCES
1. Okada, Y.; Maruyama, T.; Tamura, S.; Kameoka, H.; Masuda, S.; Tokuda, Y.; Sakai, J.; Nomura,
M. Phosphorus, Sulfur, Silicon, Relat. Elem. 2014, 189, 778-790.