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Российский химико-технологический университет им. Д.И. Менделеева

Предмет:

Методы современного органического синтеза

Файл:

МСОС Лекции с поиском и закладками

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27.01.2022

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<<< < Предыдущая 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 1718 / 1918 19 > Следующая >>>

2.2. MeTaTe3MC

MeTaTe3MC - peaK4MR npM KOTOpOH npOMCXOAMT nepepacnpeAeneHMe

u u

3aMeCTMTe/1eM npM ABOMHblX CBR3RX a11KeHOB

Cat

nepBoHa"ta/lbHO nepeKpeCHblH MeTaTe3MC anKeHOB (CM) Hawe/I npMMeHeHMe

npOMblW/leHHOM CMHTe3e anKeHOB. PeaK4MR KaTa/lM3Mposanacb CO/IRMM M KOMn/leKCaMM

Mo MW (Mo(C0)6/Al203/300°C W03/Si02*Mg0/300°C)

+	W03/Si02*MgO		II

		Joo0c

. .

2.2. MeTaTe3MC

KaTanM33TOpbl MeTaTe3MCa AJIA na6opOTOpHoro CIIIHTe3a

					,:::;-I.	-NyN		-...;::::
		II				Cl,,,Ru=--.__		...-:
		N			3	Cl	I	Ph
F3C .	o-Mo_ Ph			P(cHex)			I
F3C .		01 ==y	c1j				P(cHex)3
CF3		/\	Cl	,, u	_	KaTaJ11!13aTop
	L-CF3		Cl	I -	_	KaTaJ11!13aTop
	L-CF3			P(cHex)3		rpa66ca (2 n)
	F3			P(cHex)3		rpa66ca (2 n)
	KaTa11111JaTop		KaTa11111JaTop
		WpoKa	rpa66ca (1 n)

• Merare3111c c Kara111113aropaM111 rpa66ca He 3arpar111saerOH, C=O, COR, C02R, CONH -rpynnbl (KpOMe NH2)

0CHOBHble TMnbl peaK4MM MeTaTe3MCa

1. Cross-metathesis alkenes (CM)

2. Ring closing/opening metathesis (RCM/ROM)
	I I	RCM!>	0
	I I	ROM
		..	+

2.2. MeTaTe3MC

2. Ring closing/opening metathesis (RCM/ROM)

EtO

OEtCat. Grabbs's EtO

OEt

Cat. Grabbs's

DCM/RT

(ROM)

P/==\Ph

Pli

(RCM)

Cat. Grabbs's

DCM/RT

::::,_ (RCM)

3K3anbTOflVIA

3. Acyclic diene metathesis polymerization (ADMET) and ring o,pening metathesis

polymerization (ROMP)

Cat. Grabbs's

-....:

---

\,=J

DCM/RT

Cat. Grabbs's

(ROMP)

polynorbornene

DCM/RT

Cat. Grabbs's

Oct

(ADMET)

Oct

PDCPD

3. PeaKU.MM 3nMMMHMpoeaHMff

•Aer111Apara4111io npoBOART HarpesaHHeM s npt1cyrcrs111111 H3P04, H2S0,v HBr, HCI, {C02H)2

•3nMMMHMpoeaHMe e t<HcnoH cpeAe nporet<aer no El, no3TOMY pea1<4111R nporet<aer c

HM3KOM perMoceneKTMBHOCTblO Ill MO>KeT ocno>KHRTbCR neperpynnMpOBK3MM

OH H2S04/15Q°C

	H S0	/15o0c	-	+
	2	4	-	+
	2	4

I	OH			1
				1

	4 •		1
	•
	0	+						0
	H2S04/15o c
OH	>=<			HO	OH	2	.
OH	20		1	HO	OH			1

							•

• MeTOA 3<l><l>et<TMBeH AnR non'('-leHMR CMMMeTpM HblX anKeHOB 6e3 4uc-/mpaHC-M30MepMM

3.PeaKU.MM 3nMMMHMpoeaHMff

3.1Aer111Apara4111R cn111ptoe

• MeTOA 3<l><l>eKTHBeH AJlfl nony1.1eHHfl CHMMeTpHI.IHblX anKeHOB HnH anKeHOB 6e3 quc-/mpaHC-H30MepHH

MgBr

Meo-, - -

MeO---<I/ o

---•► Meo---<//- )-_JJ

,Qi-1MecTpOJ1

0 NMe2

Et Ph

BrMg h

Ph Ph

Et >-+-OH

-mpaHc-

Pli

2.H

1'130Mep

0_;-NMe

TaMOKC111Q)eH0_;-NMe2

3.PeaKU.MM 3nMMMHMpoeaHMff

3.1Aer11tApa1a4111R cn111ptoe

::,-

,. :::::,-

	1.	MgCI
	1.
				Cl			H3P04/T
--	,.....-N		,.			...-:::	,.
					::,-_	...-:::
						N
:	2.H®					N
	2.H®
A Cl						N'\.
A Cl							H20	::,-
N	PhMe/T					N--	H20	::,-	N--
-- c1		oet					NaOH Cl
							)Ii

N	Knap111r111H	N	N
		N
		3p111yc
		3p111yc	H
		0AOEt

3.PeaKU.MM 3nMMMHMpoeaHMff

3.1Aer111Apa1a4111R cn111ptoe

•PeareHT 6yprecca no3BOnReT npOBOAHTb AerHApara4Hto cnHpTOB B MRrKHX ycnOBHRX no Ei-MexaHH3MY (CUH-3neMMHHpOBaHHe)

O=C=N-flS-CI

011

MeOH

0 ?i

'fu

.OH

-""tr<,.

(

----IJlr►

C-N-S-N.::..t;t

)II

) 'H-

NEt3

MeO

''c-eN--SI

THF/T -

PeareHT 6yprecca

l o

t3Me

C-N-s-

MeO

11-

0	0
	OMe
	NHCbz

	\		0
	C-N-S-N-Et						Jl
Meo			O	Et	OJ"		Jl
/			II	I	\	p
						......_
	THF/30°C					......_	...
						96%
						96%
	\		0 fl	,&
	C-N-S-N-Et				N		0
Me0		/	II	I	N
Me0			O	Et	-.;;:::		OMe
	THF/60°C						OMe
	THF/60°C					92%	NHCbz
						92%	NHCbz

3. PeaKU.MM 3nMMMHMpoeaHMff

3.1 Aer111Aparau.111A cn111proe

• 6onee 34>4>eKTIIIBHO 3nlllMIIIHIIIPOBaHllle npoTeKaeT nyreM TpaHc<f>opMau,111111 OH rpynnbl B nyl.fWYIO YXOARl..l4YIO rpynny (Cl, OTs, OCOR, OCS2R)

Mel

H••

t-BuOK

)II

\..

-......,-:1•►

0--<sK

- O=C=S

.--..,. :

'HSMe

---11•

AcONa

O'l

4so0c

0AcCI

► Cl

,JI

---1)11►

A0o-H

3.2. Aer111AporanoreH111poeaH111e >=<

B-HX/T•

• 3n111M111H111posaH111e ranoreHOBOAOPOAa npoTeKaeT KaK p-3n111M111H111posaH111e np111 HarpesaHIIIIII C ClllnbHblMIII OCHOBaHlllffMIII (MeONa, tBuOK, KOH, DBU, DABCO, XIIIHOnlllH).

	K		° ..			Ill(
	H	f H	t-BuOK		r	t-BuOK	H f H
	,Br,,,,	Br	100 c	Br	r	100°c	Br''K
9		M830·	-HBr			-HBr	Br
							mpeo-

3. PeaKU,MM 3nMMMHMpoeaHHfl

3.2. Aer1>1Apora11oreHMpoeaH111e

..J

....><o

TFA

t-BuOK

•

1so0c

Meo

MeO

• DBU - no3eo11ReT npoeOAHTb AerHAporanoreHHpoeaHHe e MRrKHX yc110BHRX, AHranoreHHAbl A3IOTrpaHC-BHHH/lranoreHHAbl

THPO		THPO	1.NaBr/DMSO/T THPO	Ts 1.Nal/DMF/T	THPO
THPO		THPO		Ts 1.Nal/DMF/T	THPO	....._,,,
	+		2.t-BuOK/DMSO/So0c	2. DBU/DMF/90°c		....._,,,
	+
60%		40%				80%
60%		40%

IDBU

I ---1--► .

100°c BO%

15 min

• AHAerHAporanoreHHpOBaHHe B 3/lKHHbl npoTeKaeT o6 4HO B 6011ee >KeCTKHX YCllOBHRX KOH, EtONa, NaNH2/170-180°C H/IH PTC

_ fl	Br2/CCl4	Br	O	.	O
_ fl	Br2/CCl4			NaH/EtOH
Ph OEt		y	II	..	Ph---==--
		y	II	..
		OEt		T
		Ph	-:		O	Et
			Br			Et

4. PeaKU,MM Ba.1n1i1ra M XopHepa

4.1. PeaK4MR BttTTMra - peaK4HR Kap60HHnbHblX COeAHHeHHM C HnHAaMH c1>occ1>0pa (peareHTaMH BHTTHra), npHBOARW,aR K o6pa30BaHHto anKeHOB

1			3			1	3
J=O		® R			)II,	R	R

R	+ Ph P		4
R2	3		R		3	z==<
						R2	R4
				O=PPh

• peareHTbl BHTTHra AOcrynHbl 1,13 ranoreHonpo1113eoAHblX 111 PPh3

PPh	©	R	0			® 9R		•	R4
PPh	©	R	0			® 9R		•	R4
3	_L.-H			B(BuLi)					3
		R4		-BH		Ph P			Ph
-- P P			X		-..	Ph P			3P=<
		3	X		-..	11111111A	3 ti(		R
		3				3	3 ti(
							R4
									c:pocc:popaH

• CrepeOXHMHfl anKeHOB 3aBHCHT OT peaK4HOHHOM cnoco6HOCTH peareHTOB BHTTHra. PeaY»4-\HOHHOcnoco6Hble (HeCTa6111n1,131,1poeaHHble) HnHAbl npeHMyw,ecreeHHO AatoT Z-(4111c-) anKeHbl

...

O·PPh3

(±)

PPh

...

PPh3 ...

MeiJn L;

00,

,LK

(±)S

a./

L'.

(±)PPh3

0PPh3

I,;

-OPPh3

CKoweHHbllll OKCacj)ocq:>eTaH

Z (t(UC)-

<<< < Предыдущая 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 1718 / 1918 19 > Следующая >>>

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