Xiyama birikmasi

Xiyama birikmasi - bu uglerod-uglerod bog'larini (C-C aloqalari) hosil qilish uchun organik kimyoda ishlatiladigan organosilanlarning organik galoidlar bilan palladiy katalizli o'zaro bog'lanish reaksiyasi. Ushbu reaksiya 1988-yilda Tamejiro Xiyama va Yasuo Xatanaka tomonidan kimyoviy va regioselektivlik bilan sintetik ravishda uglerod-uglerod aloqalarini shakllantirish usuli sifatida kashf etilgan.^[1] Xiyama birlashmasi turli xil tabiiy mahsulotlarni sintez qilish uchun qo'llanilgan.^[2]

{\begin{matrix}{}\\{\ce {{R-SiR''_{3}}+R'-X->[\mathrm {F^{-}} ][{\text{Pd cat.}}]R-R'}}\end{matrix}}

${\ce {R}}$ : aryl, alkenyl or alkynyl
${\ce {R'}}$ : aryl, alkenyl, alkynyl or alkyl
${\ce {R''}}$ : Cl, F or alkyl
${\ce {X}}$ : Cl, Br, I or OTf

Reaksiya tarixi

Xiyama muftasi boshqa organometalik reagentlar bilan bog'liq muammolarga qarshi kurashish uchun ishlab chiqilgan. Organosilikonning dastlabki reaktivligi aslida Xiyama tomonidan birinchi marta xabar qilinmagan, chunki Kumada quyida ko'rsatilgan organoflorosilikatlar^[3] yordamida ulanish reaksiyasini xabar qilgan. Organosilanlar keyinchalik Xiyama tomonidan ftorid manbai tomonidan faollashtirilganda reaktivlikka ega ekanligini aniqladi.^[4]^[5] Ushbu reaktivlik palladiy tuzi bilan birlashganda, organik halid kabi elektrofil uglerod bilan uglerod-uglerod aloqasini hosil qiladi. Organomagniy (Grignard reagentlari) va juda reaktiv va past kimyoselektivligi ma'lum bo'lgan organometalik reagentlar kabi yaxshi qo'llaniladigan organometalik reagentlarning o'ziga xos muammolari bilan taqqoslaganda, organosilikon birikmalari faol emas. Rux, qalay va bor kabi metallardan foydalanadigan boshqa metall organometalik reagentlar reaktivlik muammosini kamaytiradi, lekin har bir reagent bilan bog'liq boshqa muammolar mavjud. Organozink reagentlari namlikka sezgir, organotin birikmalari zaharli, organobor reagentlari esa oson topilmaydi, qimmat va ko'pincha barqaror emas. Organosilanlar oson mavjud bo'lgan birikmalar bo'lib, ular ftorid yoki asosdan faollashganda (organotin yoki organobor birikmalari kabi) kimyoviy va regioselektiv tarzda CC aloqalarini hosil qilish uchun organogalidlar bilan reaksiyaga kirishishi mumkin. Birinchi xabar qilingan reaksiya palladiy katalizatori ishtirokida oson hosil bo'lgan (va faollashtirilgan) organosilikon nukleofillar va organogalidlarni (elektrofillar) ulash uchun ishlatilgan.^[1] Ushbu kashfiyotdan beri turli guruhlar tomonidan ushbu reaksiya doirasini kengaytirish va organosilanning ftorid faollashuvi zarurati kabi ushbu birinchi birikma bilan bog'liq muammolarni "tuzatish" uchun ish olib borildi.

Xiyama muftasini ishlab chiqish uchun silikat birikmasi pretsedenti^[3]

Reaksiya mexanizm

Organosilan ftorid (TBAF yoki TASF kabi tuzlar kabi) yoki asos bilan faollashtirilib, transmetalatsiya bosqichida C-Si aloqasining uzilishiga imkon beradigan darajada barqaror bo'lgan besh valentli kremniy markazini hosil qiladi.^[6] Ushbu asosiy oraliq mahsulotni shakllantirishning umumiy sxemasi quyida ko'rsatilgan. Bu bosqich in situ yoki reaksiyadagi katalitik aylanish bilan bir vaqtda sodir bo'ladi.

Xiyama bog'lanish mexanizmi katalitik siklni, shu jumladan A) oksidlovchi qo'shilish bosqichini kuzatib boradi, bunda organik galloid palladiyga qo'shiladi va metallni palladiydan (0) palladiyga (II) oksidlaydi; a B) transmetallanish bosqichi, bunda C-Si bog'i uziladi va ikkinchi uglerod bo'lagi palladiy markaziga bog'lanadi; va nihoyat C) reduktiv eliminatsiya bosqichi, bunda C-C bog'i hosil bo'ladi va palladiy tsiklni qaytadan boshlash uchun o'zining nol valentli holatiga qaytadi.^[7] Katalitik sikl quyida ko'rsatilgan.

Hiyama ulanishining katalitik aylanishi

Qo'llash doirasi va cheklovlari

Qo'llash doirasi

Xiyama birikmasi C_sp2 -C_sp2 (masalan, aril -aril) va C_sp2 -C_sp3 (masalan, aril- alkil) bog'larini hosil qilish uchun qo'llanilishi mumkin. Yaxshi sintetik rentabellik aril galogenidlar, vinilgalogenidlar va allilik galogenidlar va organo yodidlarning ulanishi bilan olinadi. Ushbu reaksiyaning doirasi Scott E. Daniya tomonidan o'rta o'lchamdagi halqalarni yopish uchun kengaytirildi.^[8]

Hiyama ulanishi halqani yopish reaksiyasi sifatida^[8]

Alkilgalogenidlarni organo-galo-silanlar bilan muqobil organosilanlar sifatida ulash ham amalga oshirildi. Organoklorosilanlar aril yodidlarga qaraganda ko'p va odatda tejamkor bo'lgan arilxloridlar bilan bog'lanish imkonini beradi.^[9] Nikel katalizatori GC Fu va boshqalar tomonidan xabar qilinganidek, organotrifluorosilanlarning yangi reaktivligiga kirish imkonini beradi.^[10] Ikkilamchi alkilgalogenidlar aril silanlar bilan birlashtiriladi^[11], bu reaksiya yordamida yaxshi hosil beradi.

Nikel-katalizli Hiyama muftasi GC Fu va boshqalar tomonidan kashf etilgan.

Cheklovlar

Xiyama birikmasi organosilikon reagentini faollashtirish uchun ftoridga bo'lgan ehtiyoj bilan cheklangan. Ftorid qo'shilishi organik sintezda tez-tez ishlatiladigan kremniyni himoya qiluvchi guruhlarni (masalan, silil efirlarini^[12]) parchalaydi. Ftorid ioni ham asosiy hisoblanadi, shuning uchun asosiy sezgir himoya guruhlari, kislotali protonlar va funktsional guruhlar ushbu faollashtiruvchi qo'shilishi bilan ta'sir qilishi mumkin. Ushbu reaksiyaga oid faol tadqiqotlarning aksariyati ushbu muammoni chetlab o'tishni o'z ichiga oladi. Ushbu muammoni hal qilish uchun ko'plab guruhlar faollashtirish uchun boshqa asosiy qo'shimchalardan foydalanishni yoki boshqa organosilan reagentini birgalikda ishlatishni ko'rib chiqdilar, bu esa asl Hiyama ulanishining bir nechta o'zgarishiga olib keldi.

Variantlar

Xiyama muftasining modifikatsiyalaridan biri silatsiklobutan halqasidan va quyida ko'rsatilganidek gidratlangan ftorid manbasidan foydalanadi.^[13] Bu alkilsilanni ishlatishdan ko'ra alkoksisilan/organosilanoldan foydalanishga taqlid qiladi. Ftorid manbasidan foydalangan holda bu reaksiya mexanizmi ftorid manbasidan foydalanishdan qochish mumkin bo'lgan kelajakdagi reaksiyalarni loyihalash imkonini berdi.

Daniyaning silatsiklobutanlarning Xiyama birikmasining tavsiya etilgan o'tish holati^[13]

Ftoridsiz Xiyama muftalari

Xiyama muftasining ko'plab modifikatsiyalari ishlab chiqilgan bo'lib, ular ftorid faollashtiruvchisi/bazasidan foydalanishdan qochadi. Organoklorosilanlardan foydalangan holda, Xiyama asosiy faollashtiruvchi sifatida NaOH dan foydalangan holda ulanish sxemasini topdi.^[14] NaOH^[15] va hatto suv kabi yumshoqroq asoslardan foydalangan holda alkoksisilanlardan foydalangan holda o'zgarishlar haqida xabar berilgan.^[16] Ushbu mexanizmlarni o'rganish organosilanollarni ulash sheriklari sifatida ishlatadigan Xiyama-Daniya bog'lanishining rivojlanishiga olib keldi.

NaOH tomonidan targ'ib qilingan Xiyama muftasi^[14]

Ftoridsiz Xiyama muftalarining yana bir klassi Lyuis kislotasi qo'shimchasidan foydalanishni o'z ichiga oladi, bu K 3 PO 4^[17] kabi asoslardan foydalanishga yoki reaksiyani asosiy qo'shimchasiz davom ettirishga imkon beradi.^[18]^[19] Mis ko-katalizatorining qo'shilishi, shuningdek, yumshoqroq faollashtiruvchi vositadan^[17] foydalanishga imkon berishi va hatto katalitikda palladiy (II) va mis (I) aylanmasini olishi ko'rsatilgan. stexiometrik Lyuis kislotasini qo'shishdan ko'ra tsikl (masalan, kumush (I),^[18] mis (I)^[19]).

Mis ko-katalizator bilan Xiyama ulanishi^[17]

Hiyama-Daniya birikmasi

Hiyama-Daniya muftasi ning modifikatsiyasi Hiyama muftasi bu organosilanollar va organik galogenidlarni biriktiruvchi sherik sifatida ishlatish uchun ftorli qo'shimchani talab qilmaydi. Umumiy reaksiya sxemasi quyida keltirilgan bo'lib, unda br / ' Nsted bazasini aktivlovchi modda sifatida ftoriddan farqli o'laroq, metall markazida fosfin ligandlar ham ishlatiladi.^[2]

Xiyama-Daniya ulanishining umumiy sxemasi

Ushbu reaksiyaning o'ziga xos misoli reagentlar bilan ko'rsatilgan. Agar asl Hiyama protokolida bo'lgani kabi ftorid ishlatilsa, tert -butildimetilsilil (TBS) efiri yo'q qilingan bo'lar edi.^[20]

Ftorid qo'shimchalarisiz silanolni ulash misoli^[20]

Xiyama-Daniya ulanish mexanizmi

Ushbu reaksiya mexanizmini o'rganish shuni ko'rsatadiki, silonat hosil bo'lishi palladiy markaziga organosilan qo'shilishini faollashtirish uchun zarur bo'lgan narsadir. Pentavalent kremniyning mavjudligi shart emas va kinetik tahlil shuni ko'rsatdiki, bu reaksiya silonat konsentratsiyasiga birinchi darajali bog'liqdir.^[2] Buning sababi, transmetalatsiya bosqichida Pd-O aloqasi hosil bo'lgan asosiy bog'lanish, keyin uglerod bo'lagini palladiy markaziga o'tkazish imkonini beradi. Ushbu kuzatuvga asoslanib, ushbu katalitik tsikldagi tezlikni cheklovchi bosqich Pd-O bog'lanishi bo'lib, unda silonat kontsentratsiyasining ortishi bu reaksiya tezligini oshiradi (tezroq reaksiyalardan dalolat beradi).

Xiyama-Daniya birikmasining katalitik aylanishi

Yana qarang

Xush reaksiya
Kumada ulanishi
Negishi ulanishi
Sonogashira ulanishi
Harakatsiz reaksiya
Suzuki reaksiyasi
Palladiy bilan katalizlangan ulanish reaksiyalari

Havolalar

Manbalar

↑ ^1,0 ^1,1 Hatanaka, Y.; Hiyama, T. (1988). „Cross-coupling of organosilanes with organic halides mediated by a palladium catalyst and tris(diethylamino)sulfonium difluorotrimethylsilicate“. Journal of Organic Chemistry. 53-jild, № 4. 918–920-bet. doi:10.1021/jo00239a056.
↑ ^2,0 ^2,1 ^2,2 Denmark, S. E.; Regens, C. S. (2008). „Palladium-Catalyzed Cross-Coupling Reactions of Organosilanols and Their Salts: Practical Alternatives to Boron- and Tin-Based Methods“. Accounts of Chemical Research. 41-jild, № 11. 1486–1499-bet. doi:10.1021/ar800037p. PMC 2648401. PMID 18681465.
↑ ^3,0 ^3,1 Yoshida, J.; Tamao, K.; Yamamoto, H.; Kakui, T.; Uchida, T.; Kumada, M. (1982), „Organofluorosilicates in organic synthesis. 14. Carbon-carbon bond formation promoted by palladium salts“, Organometallics, 1 (3): 542–549, doi:10.1021/om00063a025
↑ Hiyama, T.; Obayashi, M.; Mori, I.; Nozaki, H. (1983), „Generation of metal-free silyl anions from disilanes and fluoride catalyst. Synthetic reactions with aldehydes and 1,3-dienes“, The Journal of Organic Chemistry, 48 (6): 912–914, doi:10.1021/jo00154a043
↑ Fujita, M.; Hiyama, T. (1988), „Erythro-directive reduction of.alpha.-substituted alkanones by means of hydrosilanes in acidic media“, The Journal of Organic Chemistry, 53 (23): 5415–5421, doi:10.1021/jo00258a004
↑ Hiyama, T. (2002), „How I came across the silicon-based cross-coupling reaction“, Journal of Organometallic Chemistry, 653 (1–2): 58–61, doi:10.1016/s0022-328x(02)01157-9
↑ Miyaura, N.; Suzuki, A. (1995), „Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds“, Chemical Reviews, 95 (7): 2457–2483, doi:10.1021/cr00039a007
↑ ^8,0 ^8,1 Denmark, S. E.; Yang, S.-M. (2002), „Intramolecular Silicon-Assisted Cross-Coupling Reactions: General Synthesis of Medium-Sized Rings Containing a 1,3-cis-cis Diene Unit“, Journal of the American Chemical Society, 124 (10): 2102–2103, doi:10.1021/ja0178158, PMID 11878949
↑ Gouda, K.-i.; Hagiwara, E.; Hatanaka, Y.; Hiyama, T. (1996), „Cross-Coupling Reactions of Aryl Chlorides with Organochlorosilanes: Highly Effective Methods for Arylation or Alkenylation of Aryl Chlorides“, The Journal of Organic Chemistry, 61 (21): 7232–7233, doi:10.1021/jo9611172, PMID 11667637
↑ Powell, D. A.; Fu, G. C. (2004), „Nickel-Catalyzed Cross-Couplings of Organosilicon Reagents with Unactivated Secondary Alkyl Bromides“, Journal of the American Chemical Society, 126 (25): 7788–7789, doi:10.1021/ja047433c, PMID 15212521
↑ Strotman, N. A.; Sommer, S.; Fu, G. C. (2007), „Hiyama Reactions of Activated and Unactivated Secondary Alkyl Halides Catalyzed by a Nickel/Norephedrine Complex“, Angewandte Chemie International Edition, 46 (19): 3556–3558, doi:10.1002/anie.200700440, PMID 17444579
↑ Greene, T. W.; Wuts, P. G. M. Protective Groups In Organic Synthesis, 3rd ed.; John Wiley & Sons: New York, 1991. ISBN 0471160199
↑ ^13,0 ^13,1 Denmark, S. E.; Wehrli, D.; Choi, J. Y. (2000), „Convergence of Mechanistic Pathways in the Palladium(0)-Catalyzed Cross-Coupling of Alkenylsilacyclobutanes and Alkenylsilanols“, Organic Letters, 2 (16): 2491–2494, doi:10.1021/ol006170y, PMID 10956529
↑ ^14,0 ^14,1 Hagiwara, E.; Gouda, K.-i.; Hatanaka, Y.; Hiyama, T. (1997), „NaOH-Promoted cross-coupling reactions of organosilicon compounds with organic halides: Practical routes to biaryls, alkenylarenes and conjugated dienes“, Tetrahedron Letters, 38 (3): 439–442, doi:10.1016/s0040-4039(96)02320-9
↑ Shi, S.; Zhang, Y. (2007), „Pd(OAc)2-Catalyzed Fluoride-Free Cross-Coupling Reactions of Arylsiloxanes with Aryl Bromides in Aqueous Medium“, The Journal of Organic Chemistry, 72 (15): 5927–5930, doi:10.1021/jo070855v, PMID 17585827
↑ Wolf, C.; Lerebours, R. (2004), „Palladium−Phosphinous Acid-Catalyzed NaOH-Promoted Cross-Coupling Reactions of Arylsiloxanes with Aryl Chlorides and Bromides in Water“, Organic Letters, 6 (7): 1147–1150, doi:10.1021/ol049851s, PMID 15040744
↑ ^17,0 ^17,1 ^17,2 Nakao, Y.; Takeda, M.; Matsumoto, T.; Hiyama, T. (2010), „Cross-Coupling Reactions through the Intramolecular Activation of Alkyl(triorgano)silanes“, Angewandte Chemie, 122 (26): 4549–4552, Bibcode:2010AngCh.122.4549N, doi:10.1002/ange.201000816
↑ ^18,0 ^18,1 Hirabayashi, K.; Mori, A.; Kawashima, J.; Suguro, M.; Nishihara, Y.; Hiyama, T. (2000), „Palladium-Catalyzed Cross-Coupling of Silanols, Silanediols, and Silanetriols Promoted by Silver(I) Oxide“, The Journal of Organic Chemistry, 65 (17): 5342–5349, doi:10.1021/jo000679p, PMID 10993364
↑ ^19,0 ^19,1 Nishihara, Y.; Ikegashira, K.; Hirabayashi, K.; Ando, J.-i.; Mori, A.; Hiyama, T. (2000), „Coupling Reactions of Alkynylsilanes Mediated by a Cu(I) Salt: Novel Syntheses of Conjugate Diynes and Disubstituted Ethynes“, The Journal of Organic Chemistry, 65 (6): 1780–1787, doi:10.1021/jo991686k, PMID 10814151
↑ ^20,0 ^20,1 Denmark, S. E.; Smith, R. C.; Chang, W.-T. T.; Muhuhi, J. M. (2009), „Cross-Coupling Reactions of Aromatic and Heteroaromatic Silanolates with Aromatic and Heteroaromatic Halides“, Journal of the American Chemical Society, 131 (8): 3104–3118, doi:10.1021/ja8091449, PMC 2765516, PMID 19199785

[Hiyama_Discovery-1] 1,0 ^1,1 Hatanaka, Y.; Hiyama, T. (1988). „Cross-coupling of organosilanes with organic halides mediated by a palladium catalyst and tris(diethylamino)sulfonium difluorotrimethylsilicate“. Journal of Organic Chemistry. 53-jild, № 4. 918–920-bet. doi:10.1021/jo00239a056.

[Denmark_Review-2] 2,0 ^2,1 ^2,2 Denmark, S. E.; Regens, C. S. (2008). „Palladium-Catalyzed Cross-Coupling Reactions of Organosilanols and Their Salts: Practical Alternatives to Boron- and Tin-Based Methods“. Accounts of Chemical Research. 41-jild, № 11. 1486–1499-bet. doi:10.1021/ar800037p. PMC 2648401. PMID 18681465.

[Kumada_Fluorate-3] 3,0 ^3,1 Yoshida, J.; Tamao, K.; Yamamoto, H.; Kakui, T.; Uchida, T.; Kumada, M. (1982), „Organofluorosilicates in organic synthesis. 14. Carbon-carbon bond formation promoted by palladium salts“, Organometallics, 1 (3): 542–549, doi:10.1021/om00063a025

[fluoride_activation-4] Hiyama, T.; Obayashi, M.; Mori, I.; Nozaki, H. (1983), „Generation of metal-free silyl anions from disilanes and fluoride catalyst. Synthetic reactions with aldehydes and 1,3-dienes“, The Journal of Organic Chemistry, 48 (6): 912–914, doi:10.1021/jo00154a043

[Hiyama_JOC-5] Fujita, M.; Hiyama, T. (1988), „Erythro-directive reduction of.alpha.-substituted alkanones by means of hydrosilanes in acidic media“, The Journal of Organic Chemistry, 53 (23): 5415–5421, doi:10.1021/jo00258a004

[Hiyama_miniaccount-6] Hiyama, T. (2002), „How I came across the silicon-based cross-coupling reaction“, Journal of Organometallic Chemistry, 653 (1–2): 58–61, doi:10.1016/s0022-328x(02)01157-9

[Catalytic_Cycle-7] Miyaura, N.; Suzuki, A. (1995), „Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds“, Chemical Reviews, 95 (7): 2457–2483, doi:10.1021/cr00039a007

[Ring_Closing-8] 8,0 ^8,1 Denmark, S. E.; Yang, S.-M. (2002), „Intramolecular Silicon-Assisted Cross-Coupling Reactions: General Synthesis of Medium-Sized Rings Containing a 1,3-cis-cis Diene Unit“, Journal of the American Chemical Society, 124 (10): 2102–2103, doi:10.1021/ja0178158, PMID 11878949

[Chlorosilanes-9] Gouda, K.-i.; Hagiwara, E.; Hatanaka, Y.; Hiyama, T. (1996), „Cross-Coupling Reactions of Aryl Chlorides with Organochlorosilanes: Highly Effective Methods for Arylation or Alkenylation of Aryl Chlorides“, The Journal of Organic Chemistry, 61 (21): 7232–7233, doi:10.1021/jo9611172, PMID 11667637

[Fu_Nickel_1-10] Powell, D. A.; Fu, G. C. (2004), „Nickel-Catalyzed Cross-Couplings of Organosilicon Reagents with Unactivated Secondary Alkyl Bromides“, Journal of the American Chemical Society, 126 (25): 7788–7789, doi:10.1021/ja047433c, PMID 15212521

[Fu_Nickel_2-11] Strotman, N. A.; Sommer, S.; Fu, G. C. (2007), „Hiyama Reactions of Activated and Unactivated Secondary Alkyl Halides Catalyzed by a Nickel/Norephedrine Complex“, Angewandte Chemie International Edition, 46 (19): 3556–3558, doi:10.1002/anie.200700440, PMID 17444579

[12] Greene, T. W.; Wuts, P. G. M. Protective Groups In Organic Synthesis, 3rd ed.; John Wiley & Sons: New York, 1991. ISBN 0471160199

[Denmark_Cyclo-13] 13,0 ^13,1 Denmark, S. E.; Wehrli, D.; Choi, J. Y. (2000), „Convergence of Mechanistic Pathways in the Palladium(0)-Catalyzed Cross-Coupling of Alkenylsilacyclobutanes and Alkenylsilanols“, Organic Letters, 2 (16): 2491–2494, doi:10.1021/ol006170y, PMID 10956529

[Hiyama_Hydroxide-14] 14,0 ^14,1 Hagiwara, E.; Gouda, K.-i.; Hatanaka, Y.; Hiyama, T. (1997), „NaOH-Promoted cross-coupling reactions of organosilicon compounds with organic halides: Practical routes to biaryls, alkenylarenes and conjugated dienes“, Tetrahedron Letters, 38 (3): 439–442, doi:10.1016/s0040-4039(96)02320-9

[Alkoxy_silane-15] Shi, S.; Zhang, Y. (2007), „Pd(OAc)2-Catalyzed Fluoride-Free Cross-Coupling Reactions of Arylsiloxanes with Aryl Bromides in Aqueous Medium“, The Journal of Organic Chemistry, 72 (15): 5927–5930, doi:10.1021/jo070855v, PMID 17585827

[Wolf-16] Wolf, C.; Lerebours, R. (2004), „Palladium−Phosphinous Acid-Catalyzed NaOH-Promoted Cross-Coupling Reactions of Arylsiloxanes with Aryl Chlorides and Bromides in Water“, Organic Letters, 6 (7): 1147–1150, doi:10.1021/ol049851s, PMID 15040744

[Hiyama_Milder-17] 17,0 ^17,1 ^17,2 Nakao, Y.; Takeda, M.; Matsumoto, T.; Hiyama, T. (2010), „Cross-Coupling Reactions through the Intramolecular Activation of Alkyl(triorgano)silanes“, Angewandte Chemie, 122 (26): 4549–4552, Bibcode:2010AngCh.122.4549N, doi:10.1002/ange.201000816

[Hiyama_Silver-18] 18,0 ^18,1 Hirabayashi, K.; Mori, A.; Kawashima, J.; Suguro, M.; Nishihara, Y.; Hiyama, T. (2000), „Palladium-Catalyzed Cross-Coupling of Silanols, Silanediols, and Silanetriols Promoted by Silver(I) Oxide“, The Journal of Organic Chemistry, 65 (17): 5342–5349, doi:10.1021/jo000679p, PMID 10993364

[Hiyama_Alkyne-19] 19,0 ^19,1 Nishihara, Y.; Ikegashira, K.; Hirabayashi, K.; Ando, J.-i.; Mori, A.; Hiyama, T. (2000), „Coupling Reactions of Alkynylsilanes Mediated by a Cu(I) Salt: Novel Syntheses of Conjugate Diynes and Disubstituted Ethynes“, The Journal of Organic Chemistry, 65 (6): 1780–1787, doi:10.1021/jo991686k, PMID 10814151

[Denmark_Paper-20] 20,0 ^20,1 Denmark, S. E.; Smith, R. C.; Chang, W.-T. T.; Muhuhi, J. M. (2009), „Cross-Coupling Reactions of Aromatic and Heteroaromatic Silanolates with Aromatic and Heteroaromatic Halides“, Journal of the American Chemical Society, 131 (8): 3104–3118, doi:10.1021/ja8091449, PMC 2765516, PMID 19199785

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