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

Предмет:

Методы современного органического синтеза

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МСОС Лекции с поиском и закладками

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<<< < Предыдущая 1 2 3 4 5 6 7 8 9 10 1112 / 1912 13 14 15 16 17 18 19 > Следующая >>>

2. OKHCJleHHe HeMeTann1,11.1ecKHMM peareHTaMH

2.2. OKHC/leHHe aKTHBHblMH 4>opMaMH KHCIIOPOAa
2.2.1.	030H 03: npHMeH.RK>T A/I.A					OKMC/leHM.R anKeHOB
	1. 0 /MeOH/ -7s c				-				1. 0 /MeOH/ -7s c
	3		0	O	-				3		0
							#
HO EareHOJ1 2. Me2S							#				0·=-'I.
HO EareHOJ1 2. Me2S			/ HO				0		0	0
	-		2 2 2				0	+	0	0	OH
	7		2 2 2					+	HO	7	OH
		OH	2. Ru0 /H		0		nenapr0Hosa51 K-ra			7
011e111HOB851 K-Ta (18.1, c/1)							nenapr0Hosa51 K-ra		A3ena111HOB851 K-Ta

2.2.Z. KMCllOPOA 0-i,/Cat - npMMeHRIOTA/lff OKMC/leHM_ff cnMpTOB

•MeTOA no3B0/1.AeT OKMC/lRTb 1° cnMpTbl B KMC/10Tbl B npMCyTCTBMM 2° {1° > 2° )

•2° cnMpTbl OKMC/lRIOTCR B KeTOHbl (e L\MK/laX aKCMa/lbHble > 3KBaTOpMa/1bHble)

OH 0

0 /Pt

OH OH

HO (a-)

NaOH

NHAc

02/P HO

Ac-0-Thr-OH

oH H

,oH

HO -

----,

myo-lno OH

2. OKHCneHHe HeMeTannHl.leCKHMM peareHTaMH

2.3. OKMcneHMe npOM3BOAHblMM rMnepeaneHTHOro MOAa

l,l,l-TpMa4eTOKCM (Aecc-MapTMH) nepMOAMHaH (TAPI, DMP) MRrKMH OKMCJ1MTeJ1b, np111MeHReMblM AnR OKMCneHMR cnMpTOB B anbAerMAbl M KeTOHbl.

AcO OAc

','-oAc

..._.J

:c20

AcONa

-----\\l/bOH•KBr03...__

TAPI (DMP) O

IBX

Acq_OAc

OAc

---:::,

/-oAc

RAR2

-e

'-:::,

1 ...

AcO

I I

5,--

cOH

•AcOH

;,.____,

DCM/RT

• +

,;_____,

0-N

MeO--......'-:::,

TAPI

Meo

'-:::,

\ 0

TAPI...

'-----<: \

,..'-..

DCM

EtO

----...1►

DCM

-,._,,, N....._

93%

KOA011HOH

TAPI Meo

Ko.ae1111-l

MeO

'-:::,

-:P

TAPI

DCM

N/2

DCM

2. OKHC/leHHe HeMeTa/1/1H4eCKHMH peareHTaMH

2.3. OKHC/leHHe npOH3BOAHblMH r111nepea11eHTHOro MOAa

nepHOAaTbl - MRrKMe OKMC/IMTe/lM, npMMeHReMble A/IR paCLl,\enneHHR C-C CBR3eM 1,2- AM4>VHKL\MOHa/1M3HpoeaHHbl)( coeAMHeHMH, - rnMKOJleH, 1,2-aMMH03TaHonoe, rMAPOKCHKeTOHOB, rHAPOKCHKMC/IOT H AP· B Kap60HH/lbHble COeAHHeHHR (peaK4MR MananpaAa)

HO	OH	0	OH	HO	OH
Rl	R2	R1	0	R1	0

0	0	0
OH	}-oH	}-oH
Rl	R1	Rl

0	0	0	CO2	CO2	NH3	0	0
}-1-1	'y--H	'y--QH	CO2	CO2	NH3	'y--H	'y--H	H
R2	R2	R2	H20	H20	CO2	R2	R2	R2
						NH3	2 NH3

R3	1R4t,	R
	H''		1
HO		OH

Nal04

1 1

R ,,, ,,,R

A +

)(

MeOH

1H'

-Nal03

o,1,,,,

-H20

o, .,,,,o

R4 R3

R 1 R2

H0'7. \'0l"I

o-4l'oNa

O'/

ONa

2. OKHC/leHHe HeMeTa/1/lH\.leCKHMH peareHTaMH

2.3. OKHC/leHHe npOH3BOAHblMH rHnepeaneHTHOro MOAa nepHoAaTbl - npMMeHeHHe Allff pacLL\en11eH11tff C-C CBR3eM

HO				-/-o	OH
				0		..	20 i H

HO D-Man	H	MeO	OMe		OH oj- MeOH
HO D-Man	H	2·	X	/TsOH	OH oj- MeOH		Glyceral

••OH

MeO,_J

"s::::::;;O

NalO

'-s::::::- '

O Meo/\

OHHO·

/TsOH

Pd/C

MeOH

LGlyceral-

______

-- AsqA

___.

PeaK4HR Ma11anpaAa -JleMHKC -A>KOHCOH - KaTa/lHTH"leCKHH eapHaHT paCLL\en11eHHR C=C cBR3eM - a11bTepHaTHBa 030HO/IH3V

.. 0	I 0
OH MeOH	H
OH MeOH	H

2. OKHcneHHe HeMeTannHl.leCKHMH peareHTaMH

2.4. OKMA ceneHa (Se02): npHMeH.RIOTAfl.R OKHC/leHH.R aKTHBHPOBaHHblX MeTH/lbHblX H MeTH/leHOBblX rpynn {c BblCOKOH CH-KHC/IOTHOCTblO) B cnHpTbl H Kap60HH/lbHble

COeAHHeHH.R {r. P1111eH).
		0			0
	'-:::::	Se02		'-:::::		0	0
I		Se02
I		A1110KcaH/i.\	I		H	Se02
					H
				0		)llllOKCaH/6	0
				0
		Se02

A1110KcaH/i.\

KapeH

......,

)II /J

2 OH

u1110

•11t1QTBDPS

1(0

1.Se02/T

A1110KcaH

---tl)II►

2.Ac20

			/J
HO	H(		'--"OH
HO		OH
	76%	OH	111HreHOJ1

111 11 11

- -<:			•11t1QTBDPS	- •►
			•11t1QTBDPS	)II
				)II
AcO	0
	1(0		Ullto
.. ..		59%
	O	59%
			0

Li1HreHon aHre11aT (n111KaTo)

H202

2. 01<111cneHHe HeMeTann111 ecKHMH peareHTaMH

nepOKCMAbl M nepOKCMKMCnOTbl

2.5. nepOKCMA BOAOPOAa (H202} WMpOKO npMMeHAIOT KaK ReOx AnA KaTanMTM'-leCKOro

OKHcneHMA: Mo {VII}, Ru{VIII}, W(VI), SeOz

OH	0
	0
RuCl3(oa1)/H202					0
-	H			HO	OH
	H
	100°/o	H20/a1111KBaT376
		H20/a1111KBaT376			3 MJlH. T/roA 0
Meo			(MeN(Oct)3CI)
Meo			(MeN(Oct)3CI)

• OKMcneHMe TM03<l>Mp0B B S-OKCMAbl

s,......- o 5,......-

I '

99%

• B eno'-IHOH cpeAe Mcno/lb3VtoT A/IA OKMcneHMR 6opaHoe "' rMAPOnM3a HMTpMnoe AO a MAOB (peaK'-'MR PaA3MWeBCKOro)

(DCM/TEAS) -:::"' I

2. 0KHCneHHe HeMeTannH'-leCKHMH peareHTaMH

nepoKCMAbl M nepOKCMKMCnOTbl

2.6. OKCOH (2KHS05*KHS04*K2S04) MOW.HblM OKMCJIMTenb, npMMeHfleMblM AJIR OKMCJleHMR cl>YHKU,MOHanbHblX rpynn M r1eHepaU,MM OKMCnMTeneM (ODO)

• 9nOKCMAMPOB3HMe anKeHOB

OKCOH 0-0

DDO

0KCOH

• OKMCJleHMe 1° aMMHOB B HMTpOCOeAMHeHMfl

NH2	N02	NH2
	50%	'
	0KCOH	"-'OMe	OKCOH

TBAS

• OKMCJleHMe TM09cl>MPOB

)<F

8 AMOKCMAbl

O I.,.F O i F

0KCOH

2. OK111cneH111e HeMeTann111'-lecK111M111 peareHTaMvt

nepOKCMAbl M nepOKCMKMCnOTbl

2.7. mpem-6yr111nrlllAPOnepOKCJ.1A (t-BuOOH, TBHP) MffrKHH OKl/lcnl/lTenb AJISI ::tnOKCIIIAHPOBaHIIIJI

anKeHOB, 111 OKIIICneHHJI 4>VHK4HOHanbHblX rpynn

0	TBHP	O	I	'-::::		Q	TBHP	'-::::
0

				.__......_
	H 0/H@/Tpl-1TOH8	,...,........,.			):=		DCE/6/24h		R
		,...,........,.			):=
					R
	2(BnNMe3CI)				R

• ReOx Anff KaTanl/lTlll eCKoro OKl/lcneHIIIJI: Cr(VI), V(VI}, Mo (VII}, W(VI}, Ti(IV}, Se02

0	'-::::	Ny Se02(Cat)			I '-::::	N
	I
TBHP				TBHP
		N	Al-10KcaH/LV!h			N/4

100%

2.7. N-MeT111nMop4>onMH N-OKCMA (NMO}

•ReOx AJISI- Os{VIII} -KaTan1113111pyeMoroOKHCJleHHJI (<<in situ» NMM+ H202)

•MflrKHH OKHCnHTenb AJlfl npespaw.eHHfl aKTMBHpoBaHHblX

ranoreHonpOlll3BOAHblX (All, Bn)	Br	0

hchekolikhln	Et NMO/MS3AMeCN	Co
		O

..........OEt

86%

2.8. AMMeTH/IAHOKCHpaH (ODO)

2. OK1,1cneH1,1e HeMeTannM'-leCKHM"1 peareHTaMM

nepOKCMAbl M nepOKCHKMC/IOTbl

BblCOKOaKTMBHblH OKHC/IMTe/lb roTOBHTCR e BMAe pacreopa B au,eTOHe (O.lM), WHpOKO npHMeHRtoT A/IR OKMC/leHHR <l>YHKU,HOHa/lbHblX rpynn

• 3nOKCMAMPOBaHHe anKeHOB

ODO

.* *.$"

"'=./

'\1

a'-'eTOH

95%

-...:::::

ODO

-...:::::

a'-'eTOH

O 100%

• ACMMMeTpH4eCKOe 3nOKCHAHPOBaHHe anKeHOB XMpa/lbHblMH AHOKCHpaHaMM

(MeTOA R. WH)

,--Q -.0

nepexo,qHoecoCToflHHe

R1 J:

0"'" -.f\ ,.,""o_ Ii

/'o - o

cat

-1

-------,....1,11111 . .

,•

(TBAS)

OKcoH/ MeCN/H20

•

.' ,•

Ph _______.., .

hchel<otlkhin

Pti Ph

95%, ee= 95%

2. OKHCneHHe HeMeTannH4eCKHMH peareHTaMH

nepOKCHAbl H nepOKCMKHCnOTbl

2.8. AHMeTHnAHOKCHpaH (ODO)

• OKHC/leHHe sp3 CH CBR3eM (3° > 2° >> 1° )

ODO	,
	,
	r--.....---:t--QH
a1.4eTOH
24 h	100%
		0
		OMe
		NHBoc
• OKHCneHHe 1,2-AHOnOB
OH		0
OH
	ODO ...
	DCM	OH 96%
OH	4h	OH 96%

• OKHCneHHe cepyCOAep>t<a HX <l>VHKL4HH

5/			O /	0
5/		..		o=\/
		..		o=\/
	ODO			ODO
				ODO

ODO ..

	000..,		Me
	000..,			..
a1.teTOH
a1.teTOH
	72 h	NHBoc		NHBoc

	OH	ODO
	,,,,
		DCM
1,,	,..	4 h	,,,,,,
			98%

<<< < Предыдущая 1 2 3 4 5 6 7 8 9 10 1112 / 1912 13 14 15 16 17 18 19 > Следующая >>>

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